CY6151 ENGINEERING CHEMISTRY-I NOTES

UNIT I POLYMER CHEMISTRY

Part – A

1. Define polymer and polymerization.

Polymers are macromolecules formed by repeated linkage of large number of small

molecules called monomers. e.g.
nCH2 = CH2 (-CH2 – CH2) - n
Ethylene (Monomer) Polyethylene (Polymer)

Polymerization is the chemical process in which large numbers of monomers combine

together, to form a polymer with or without the elimination of simple molecules like water, HCl,
etc.

2. Define condensation polymerization with suitable example.

It is a reaction between simple polar groups containing monomers that yield polymers with
the elimination of small molecules like H2O, HCl, etc.

n H2N-(CH2)6-- NH2 + n HOOC (CH2)4 COOH

Hexamethylene diamine Adipic acid

-[HN – (CH2)6 – NH – C – (CH2)4 – C] n-- + 2nH2O

|| ||
O O
Nylon 6:6 (Polyamide)

3. Define hetero chain polymer.

If the back bone of the polymer chain is made up of different atoms it is called heterochain
polymer, e.g., polyesters, Nylon 6:6. Polyesters contain carbon and oxygen atoms in the main
chain.

Explain functionality of a monomer with a suitable example.

The number of bonding sites or reactive sites or functional groups in a monomer is known as its
functionality.

CH2 = CH2 (ethylene) – Functionality is 2 (Two bonding sites are due to the presence of
one double bond in the monomer. Therefore ethylene is a bifunctional monomer).
5. What is degree of polymerization?

The number of repeating units (n) in a polymer chain is known as the degree of
polymerization. It is represented by the following relationship,

Degree of polymerization (n) = Molecular weight of the polymeric network

Molecular weight of the repeating unit

6. What is addition polymerization?

It is a reaction that yields polymer which is an exact multiple of the original monomer
molecule. The monomer contains one or more double bonds. This reaction is initiated by the
application of heat, light, pressure, or catalyst, for breaking down the double bonds of monomers.
In addition polymerization there is no elimination of any molecule.
(e.g) Polyethylene is produced from ethylene:
nCH2 = CH2 Heat / Pressure n (– CH2 – CH2 -)
Ethylene Catalyst
- (CH2 – CH2) n--
Polyethylene

7. Explain co-polymerization with an example.

It is the joint polymerization in which two (or more) different moments combine to give a
co-polymer. Co-polymerization is mainly carried out to vary the properties of polymers such as
hardness, strength, rigidity, heat resistance, etc.
n CH2 = CH – CH = CH2 + nCH2 = CH

(Butadiene) C6H5 (Styrene)

(-CH2 - CH = CH - CH2 - CH2 – CH) n -

C6H5

(SBR)
8. Why thermosetting plastics cannot be remoulded?
Thermosetting Plastic consists of three dimensional network structure where the polymer
chains are connected by strong covalent bonds by cross linking. They get hardened on heating and
cannot be remoulded.

9. What is Tacticity?
The orientation of monomeric units or functional groups in a polymer molecule can take
place in an orderly or disorderly manner with respect to the main chain is known as tacticity
10. Define Tg.
Glass transition temperature (Tg) is the temperature at which the amorphous solid state
(glassy state) is transformed to the melt state.

11. What is poly dispersity index?

The ratio of the weight – average molecular weight (M w) to that of number – average
molecular weight (M n) is known as polydispersity index (PDI).

PDI = M w/ M n

12. How are the polymers classified on the basis of their tacticity? 1. Isotactic polymers
Here functional groups are arranged on the same side of the main chain. 2. Syndiotactic
polymers
Here functional groups are arranged in an alternating fashion. 3. Atactic polymers
Here functional groups are arranged randomly.

1. What are the advantages of solution polymerization?

Exothermic heat evolved during polymerization is controlled easily.
Viscosity built up is negligible.
The mixture can be agitated easily.

2. What are the factors affecting Tg?

The value of Tg depends on chain length, extent of cross linking, the barrier which
hinders the internal rotation of the chain links.
The values of Tg of a given polymer varies with the rate of heating or cooling.
3. Below Tg the polymer is hard and brittle.
Part – B

1. Explain the mechanism of free radical polymerization. Free radical mechanism

Polymerization by free radical mechanism occurs by the following three steps,

namely, initiation, propagation, and termination.

1. Chain Initiation
.
1. Production of a pair of primary free radicals (R ) by homolytic cleavage of an initiator:
I 2R●
Initiator Free radicals

Heat is used to produce free radicals by homolytic cleavage of weaker O-O bond of the
peroxide molecule

(1) – OOCCH3
CH3COO 70- 90oC 2CH3COO● or (R●)
 Acetyl Peroxide free radicals

(2) – OOCC6H5
C6H5COO 80 – 95oC 2C6H5COO ● or (R●)
Benzoyl Peroxide

2. Addition of this free radical to the first monomer to produce chain-initiating species:
H H
| |
R● + CH2 = C R – CH2 – C ●
| |
Y Y
(Free radical) (First monomer) (Chain-initiating species)

2. Chain Propagation:

Propagation step consist of the growth of the chain-initiating species by successive addition of
large numbers of monomer molecules:

H H H H
|| | |
●
R-CH 2 -C = C
+ n CH2 R – (CH2 – C)n – CH2– C●
| | | |
YY Y Y

3. Chain Termination:

Termination of the long living radical polymer may occur either by coupling reaction
or by disproportionation

a) By Coupling or Combination:

Coupling of free radical of one chain end to another free radical chain leads to a macro
molecule.

H H H H
● ●
R — CH2 — C + C — CH2 – R R— CH2 — C — C — CH2 — R

Y Y Y Y
Macromolecule

(Dead Polymer)
 b) By Disproportionation:

Transfer of a hydrogen atom of one radical centre to another radical centre forming two
H H H H

R –CH2 – C● + ●C—CH2 –R R — C = C + H— CH— CH2— R

Y Y

Unsaturated Saturated
macromolecule macromolecule
macromolecules, one saturated and another unsaturated.

3. Distinguish thermoplastics and thermosetting plastics with suitable examples.

Thermoplastic resin Thermosetting resins

They are formed by addition polymerization They are formed by condensation

Polymerization
They consist of linear long chain polymers They consist of three-dimensional network
structure
Polymer chains are held together by weak Polymer chains are held by strong
Vander Waals forces covalent bonds
These polymer are usually soluble in organic They are usually insoluble in organic
solvent solvents
They can be remoulded and recycled They cannot be remoulded or recycled

They can be softened on heating and hardened on They get hardened on heating and they
cooling reversibly. cannot be softened on reheating

2. Distinguish between addition and condensation polymerization

Addition Polymerization Condensation Polymerization

The monomer should have at least one The monomer should have at least two
multiple bond, e.g., identical functional groups

CH2 = CH2 (ethylene) CH2 – OH

| (glycol)
 CH2 – OH
H2 N(CH2)6 COOH
(6-aminohexanoic acid)

Monomer adds to give a polymer and no
other by-product is formed.
Number of monomeric units decreases
steadily throughout the reaction as there is
steady growth of polymer chain.
High molecular weight polymer is formed
at once.
Usually thermoplastics are produced,
e.g., polyethylene, PVC, etc.
This follows a free radical mechanism.
Homochain polymer is obtained.
Monomers condense to give a polymer and
by-products such as H2O, CH3OH, are
formed.
Monomers disappear at the early stage of
reaction as oligomers are formed first and
then polymers are produced
Molecular weight of the polymer rises
steadily throughout the reaction.
Usually thermosetting plastics are
produced, e.g., Bakelite, urea-
formaldehyde.
This follows the mechanism of
condensation reaction
Hetero-chain polymer is obtained.

3. Give the preparation, properties, and uses of:

1. Nylon – 6:6
It is obtained by the polymerization of adipic acid with hexamethylene diamine:
H2N (CH2)6 NH2 + HOOC (CH2)4 COOH

Hexamethylenediamine Adipicacid

Condensation polymerization
21

N – (CH2)6 – N – C - (CH2)4 – C -–– -

H H O O
n Polyhexamethylene adipate)

Properties

1. Nylon is tough, strong, and easily mouldable.

2. It has good chemical resistance and low co-efficient of friction.
3. Insoluble in common organic solvents but soluble in phenol and formic acid.
4. It has high thermal stability.

Uses

1. Nylon is used to make textile fibers for use in dresses, socks, carpets, etc.
2. It is used for making filaments for ropes, tooth brush, etc.
3. It is used for making tyres, watch straps.
4. It is a good substitute for metal in gears and bearings.

Epoxy resin:
Preparation:

Epoxy resin is prepared by condensing epichlorohydrin with bisphenol.

CH3

n HO C OH + Cl – CH2 – CH – CH2
CH3 O

Bisphenol Alkaline catalyst

- nHCl

CH3

O C O CH2 CH CH2
CH3 OH n

Epoxy resin

22
 Properties

1. It has high chemical – resistance to water, acids, alkalis, various solvents and other chemicals.
2. They are flexible, tough and possess very good heat resisting property.
3. Due to the polar nature of the molecules, they possess excellent adhesion quality.
Uses:
iii) It is used as surface coatings, adhesives like araldite, glass- fiber reinforced Plastics.
iv) It is applied over cotton, rayon and bleached fabrics to impart crease-resistance
and shrinkage control.
3. It is used as laminating material in electrical equipments.

4. Write notes on bulk and suspension polymerization techniques.

Bulk polymerization
The monomer is taken in a liquid form and the initiator, chain transfer agents
are dissolved in it .The flask is placed in a thermostat under constant agitation and heated.

Monomer + Initiator + chain transfer agent polymer

(Liquid) (Mixed with monomer)
(Hydrogen atom donor)
The reaction is slow but becomes fast as the temperature rises. After a known period of time, the
whole content is poured into methanol and the polymer is precipitated out.
Examples: polystyrene, PVC, PMA.

Advantages:

1. It is simple and requires simple equipments.

2. The polymer has high optical clarity.

3. High-purity polymers are obtained.

Disadvantages:

1. During polymerization, viscosity of the medium increases hence mixing and control
of heat is difficult.
23

2. Polymerization is highly exothermic

Uses: It is used in casting formulations, adhesives, plasticizers and lubricant and additives.

Suspension Polymerization:
 It is used only for water insoluble monomers. This polymerization reaction is carried
out for heterogeneous systems.

The water insoluble monomer is suspended in water as tiny droplet and an initiator is dissolved in
it by continuous agitation. The suspension is prevented from coagulation by using suspending agents
like PVA, gelatin, methyl cellulose. The whole content is taken in a flask and heated at constant
temperature with vigorous agitation in a thermostat in nitrogen atmosphere. After eight hours pearl-
like polymers are obtained, which is filtered and washed by water.

Monomer + Initiator + suspending agent polymer

(Suspension (dissolved (suspended in
in water) in monomer) water as beads)

Examples: polystyrene, polystyrene- divinyl benzene.

Advantages:

1. Products are highly pure.

2. This method is more economical.

3. Efficient heat control.

4. Isolation of product is easy.

Disadvantages:

1. It is only applicable for water insoluble monomers.

2. Control of particle size is difficult.

Uses: 1. it is used as ion exchangers.

2. This technique is used in heterogeneous system.

1. How are solutions and emulsion polymerization carried out? Mention some applications
Solution polymerization:

The monomer, initiator and the chain transfer agents (Hydrogen atom donor) are taken in
a flask and dissolved in an inert solvent. The whole mixture is kept under constant agitation. After
some time, the polymer is precipitated by pouring it in a suitable non-solvent.

Monomer + Initiator + chain transfer agent polymer

(Dissolved in (Dissolved in (In solution)
 inert solvent) inert solvent)

Examples: Polyacrylic acid, polyisobutylene and polyacrylonitrile.

Advantages:

1. Heat control is easy.

2. Viscosity built up is negligible.

3. The mixture can be easily agitated

Disadvantages:

1. It requires solvent recovery and recycling.

2. It is difficult to get very high molecular weight polymer.

3. The polymer formed is isolated from the solution either by evaporation of the solvent
or by precipitation in a non- solvent.

Applications:

It can be directly used as adhesives and coatings.

Emulsion polymerization:

The monomer is dispersed in a large amount of water and then emulsified by the addition of
soap. Then initiator is added. The whole content is taken in a flask and heated at a constant
temperature with vigorous agitation in a thermostat with nitrogen atmosphere. After 4 to 6 hours,
the pure polymer can be isolated from the emulsion by addition of de-emulsifier like 3% solution
of Al2(SO4)3.

Monomer + Initiator + surfactant polymer

(Dissolved in (water soluble) (Emulsion in water)
inert solvent)

Advantages:
1. The rate of polymerization is high.
2. Heat can be easily controlled and hence viscosity is low.
25

3. High molecular weight polymer can be obtained.

Disadvantages:
1. It is very difficult to remove entrapped emulsifier.
2. Polymer needs purification.
3. It requires rapid agitation
Applications:
1. It is used in production like water based paints, adhesives, plastics, etc.,
 2. It is used for the manufacturing polymers like butadiene and chloroprene.

6. Explain the mechanism of anionic polymerization with an example.

This type of polymerization takes place when electron withdrawing groups like

Cl, CN is present in a monomer. These groups stabilize the carbanion.

Examples: Vinyl chloride, styrene, acrylonitrile.

The catalyst used to initiate the reaction are Lewis bases like NaNH2, LiNH2 etc.,

(i) Initiation

It involves the formation of chain initiating species.

KNH2 K+ + NH2 -

H H H H

NH2 - + C = C H 2N – C – C
-

H CN H CN

ii) Propagation

It involves the growth of chain initiating species by successive addition of

large number of monomers and the negative charge simultaneously shifts to the newly added
monomer.

HH H H H H H H

NH2 - C –C - + n C = C H2N (C – C) n – C – C - ( Growing chain)

H CNH CN H CN H CN

(iii) Termination

Termination of the growing chain occurs by adding ammonia.

H H H H

NH2 ( C – C) n C-C- + H NH2

 H CN H CN

H H H H

NH2 (C – C ) n – C – C – H + NH2 -

H CN H CN

7. Explain the mechanism of cationic polymerization with example Cationic Polymerisation:

This type of polymerization takes place when electron donating groups like CH3, C6H5
are present in monomers. The catalyst used to initiate the reaction is Lewis acid like AlCl 3, BF3
with co-catalyst water.

Cationic Polymerization occurs in three major steps.

1. Initiation
2. Propagation
3. Termination
Initiation:

It involves the formation of chain initiating species.

AlCl3 + H2O H+. AlCl3OH-

Catalyst Co-catalyst

H H H H
 27

C = C + H+.AlCl3OH- H– C – C +. AlCl3OH-

H C6H5 HC6H5
Chain initiating species

Propagation:

It involves the growth of chain initiating species by successive addition of large number of
Monomers.

H H H H

+. - nC = C
H – C – C AlCl3OH +

H C6H5 H C6H5
H H H H

H – (C – C)n – C – C +.AlCl3OH-

H C6H5 H C6H5

Growing Chain

Termination

Termination of the growing chain involves removal of the catalyst by the addition of proton to the counter
ion AlCl3OH-

H H H H HH H H

H – ( C – C )n –C – C +.AlCl3OH- H– ( C – C ) n – C = C + H+.AlCl3OH-

H C6H5 H C6H5 HC6H5 C6H5

Macromolecule

8. Explain Glass transition temperature (T g) and mention its factors influencing it.

Glass transition temperature is the temperature at which the amorphous solid state is transformed
into glass state. Below the glass transition temperature (T g) the polymer is hard and above which is
soft. The hard brittle state is called glassy state and soft flexible state is called as rubbery or
viscoelastic state. Thus the glass transition temperature is an important property of a polymer.
 28

Factors influencing T g

1. Molecular weight: The glass transition temperature of a polymer is influenced by its

molecular weight. As the molecular weight increases the Tg also increases.
2. Flexibility: A free rotational motion of the polymer chain imparts flexibility to the polymer.
As flexibility decreases the Tg of the polymer increases.
3. Crystallinity: Higher the crystallinity, larger is the Tg value of a polymer. In crystalline polymer,
the linear or stereo-regular chains are lined up parallel to each other and are held by strong
cohesive forces. This leads to a high Tg value of the polymer.
4. Plasticisers: This when added to polymer improves the flexibility and reduces brittleness and
Tg.

9. Discuss about Stereo specific polymer (or) Tacticity

The special orientation of groups in a polymer molecule can be in an order (or) disorder with
respect to main chain and this is known as Tacticity.

The three types of stereo - regular polymers are

Isotactic polymer: If the groups attached to the carbon are arranged on the same side of the main
chain, the polymer is called Isotactic polymer.

Syndiotactic polymer: If the groups attached to the carbon chain are arranged in an alternating
side of the main chain, the polymer is called Syndiotactic polymer.

Atactic polymer: If the groups attached top the carbon chain are arranged randomly, the polymer
is called Atactic polymer.

12. Explain about number average and weight average concept of Molecular weight of a

Polymer.

Assume that there are total n number of molecules in a polymer sample and ni of them have
M1 molecular weight; n2 have M2 molecular weight and so on till we get ni having Mi
molecular weight.
Now we have total number of molecules (n) is given by

n = n1 + n2 ------ + ni = ∑ni
Number of Polymer molecules in fraction 1 = n1

Number fraction of fraction 1 n1=

∑ni

n11M=1
Polymer Molecular weight contribution by fraction
 ∑ni

Similarly molecular weight contribution by other fractions will be

= n2M2 , n3M3, ….. niMi

∑ni ∑ni ∑ni

Number average molecular weight of the whole polymer will be given by

Similarly, Total weight of the polymer =W = ∑ niMi

Weight of polymer fraction 1 = W1 = n1M1

Weight of polymer fraction of fraction 1 = n1M ni M

=i

W ∑ni Mi

Polymer Molecular weight contribution by the other fractions will be

n2M2n23M
, 32 ….. niMi2
∑niMi
∑niMi ∑niMi

The weight average molecular weight for all polymer fractions will be then (Mw)

n1M12 + n2M22 +…..+ niMi2 = ∑ niMi2

∑niMi ∑niMi ∑niMi ∑niMi
12. Explain the Polydispersity index of a polymer

A simple chemical compound contains molecules of same molecular weight, such

system is called mono dispersed system. For example water contains H2O molecules of
molecular weight of 18. A polymer which contains molecules of different molecular
weight is called as polydispersed system. This is due to the variation in the degree of
polymerization. The polydispersity of a polymer can be well understood by a simple
molecular weight distribution curve (ni Vs Mi).

The ratio of the weight – average molecular weight (M w) to that of number – average
molecular weight (M n) is known as polydispersity index (PDI). The PDI is always more than 1

PDI = M w/ M n
Unit – II CHEMICAL THERMODYNAMICS
PART-A
1. Define System
A system is defined as any specified portion of matter under study which is separated from
the rest of the universe with a bounding surface. A system may consists of one (or) more
ssubstances.

2. Define Surroundings
The rest of the universe which might be in a position to exchange energy and matter with
the system is called surrounding. Ex. Surroundings imply air (or) a water bath in which a
system under examination is immersed.

3. Define Isolated System

A system which cannot exchange both energy and matter with its surroundings is called
and isolated system.
Example: Consider a system consisting 100ml of water in contact with its vapour in a
closed vessel. Since the vessel is closed no matter (liquid or vapour) can enter or leave the
vessel. Further if the vessel is also insulated (as shown in the fig) the vessel cannot lose or
gain heat from the surroundings.

4. What is an Isothermal Processes.

Those processes in which the temperature remains fixed are termed as isothermal process.
This is achieved by placing the system in a thermostat i.e. dT=0

5. Define Cyclic Processes

When initial and final states of a system in a process are the same the process is called a
cyclic process. In this process, a system undergoes various processes and returns back to
its initial state. i.e. dE=0, dH=0.Define Intensive and extensive property Intensive
property The property which do not depend on the amount of substance but
depend only on nature of the susbstance present in the system are called intensive
property. Example: Temperature, pressure, concentration and density.

Extensive property
The proeperty which depend on the amount of substance present in the system is called
 extensive property.
Example: Mass, volume , energy, Internal energy (E), enthalpy(H), entropy(S), Free
Energy(G).
8. Define Internal Energy Change (∆E) Internal Energy Change (∆E)
Change in internal energy depend on initial and final states of the system and does not depend
on intermediate states.
Thus, the internal energy change (∆E) is defined as the difference in the internal energies of
initial and final states of the system. Thus,

For Chemical reaction

9. Define Enthalpy
Enthalpy is defined as “the sum of internal energy and pressure-volume energy of a system
under a particular set of conditions”.
i.e. H = E + PV (1)

10. Define Enthalpy change

Enthalpy Change (∆H)
Like internal energy, enthalpy also cannot be measured, but change in enthalpy (∆H) can be
measured from the differences in the enthalpy of initial and final state of the system.
Definition
The enthalpy change (∆H) is defined as the difference in the enthalpy of initial and final states
of the system. Thus,

∆H = H2 – H1 (2)
But for chemical reaction

Substituting the values of H2 and H1 from equation(1) to equation(2) We get

= (E2 – E1) ― (P2V2 – P1V1)

∆H = ∆E − P∆V (3)
Equation (3) is the equation for change in enthalpy at constant pressure

11. State the law of conservation of energy.

The law of conservation of energy states that “ Energy can neither be created or destroyed
but it can be transformed from one form to another form “.

12. Give the mathematical expressions for the First Law of thermodynamics
The mathematical expression of First Law of thermodynamics is
∆E = q – w (or) dE = q − P∆V

13. State II law of thermodynamics. Represent by a mathematical equation. Clausius

Statement: It is impossible to construct a machine which will transfer heat from a lower
temperature (cold body) to a higher temperature (hot body).
It is mathematically stated as

14. Define Entropy

It is a measure of randomness or disorderness in a molecular system

15. Define the term ‘standard free energy’. Illustrate with an example.
It is defined as “The free energy change for a process at 25⁰C in which the reactants are
converted into the products in their standard states.”. Thus,

The value of ∆G⁰ can be calculated for a reaction from the standard free energies of formation
(∆G⁰f)

16. Calculate the change in entropy accompanying the isothermal expansion of 4 moles
of an ideal gas at 300K until its volume has increased three times.
Entropy change in an isothermal expansion of an ideal gas

Given:
V1 = 1, V2 = 3; n=4; R=1.987cals

=8.733 cals

17. Define Spontaneity

It is defined as the tendency of a process to occur naturally is called the spontaneity.

3. How does the entropy of system changes

When a gas is liquefied
Ice is melted
(a) When a gas is liquefied, entropy decreases
(b) When ice is melted, entropy increases

19. What are the conditions for a process to be spontaneous based on the relation
∆G=∆H−T∆S.
∆H = negative & ∆S = positive
∆H = negative & ∆S = negative at low temperature ∆H = negative & ∆S = positive at high
temperature

20. Predict whether the following reaction is spontaneous at 25⁰C

C(s) + H2O(l) CO(g) + H2(g)
∆H=31.4kcal/mole and ∆S=32cal/deg at 25⁰C
We know that
∆G=∆H−T∆S
Given
 ∆H=31.4kcal; ∆S=32cals (or) 0.032k.cals , T=25 + 273 = 298K

On substituting these values in the above equation

∆G=∆H−T∆S
= 31.4 – 298(0.032) = 31.4 – 9.536
∆G=21.9k.cals.
Since, ∆G is positive rhe reaction is non-spontaneous.

21. ∆G for a reaction at 300K is −16.0kcal, ∆H for the reaction is −10.0k.cal. What is the
entropy change for this reaction.
Solution
We know that
∆G = ∆H − T∆S

Given:
∆H = −10.0 k.cals; ∆G = −16.0 k.cals; T = 300 K

20cals.K-1

2. What is the influence of ∆H and ∆S values in the spontaneity of the reaction?

b) If ∆H is negative and ∆S is positive then the process will be spontaneous as ∆G is
negative.
c) When both ∆H and ∆S are positive, at higher temperature, ∆G will be negative and the
process will be spontaneous.

3. What is Clausius inequality?

The cyclic integral of is always less than (or) equal to zero.
(or)
The amount of heat transferred to the system divided by its temperature is equal to or less than
zero is known as clausius inequality.

24. According to Clausius, what is value for reversible heat engine and
irreversible heat engine.
(i) For reversible heat engine
(ii) For irreversible heat engine

25. What is Helmholtz work function (A)?

The part of the internal energy of a system can be used at constant temperature to do useful
work. This part of internal energy which is isothermally available is called work function of the
system A=E – TS

26. What is the significance of free energy?

The decrease of free energy (−∆G) of a process at constant temperature and pressure is equal
to the useful work obtainable from the system.
27. Write Gibbs-Helmholtz equation? What is its application?
Gibbs-Helmholtz equation is

(or)

Applications
(i) Enthalpy change (∆H) for the cell reaction can be calculated
(ii) Entropy change (∆S) can be calculated
(iii) It is used to calculate ∆H from values of free energy change at two different
temperature.

28. Give the relation between (i) ∆H & ∆G, (ii) Emf & ∆G

(ii)−∆G=nFE

29. What is the significance of Gibbs Helmholtz equation? What are its applications.
Significance: It relates the free energy change (∆G) to the enthalpy change (∆H) and the rate of
change of free energy with temperature at constant pressure.
Applications:
1. Calulation of enthalpy change (∆H) for the cell reaction

2. Calculation of Emf of the cell

3. alculation of free energy change (∆G) ∆G=∆H−T∆S

30. Prove that (∂S/∂P)T = −(∂V/∂T)P

Gibbs free energy G is defined as
G = H−TS
dG = dH−TdS−SdT

But H = E + PV
dH = dE + PdV + VdP
= TdS + VdP (since, TdS = dE + PdV)

Thus, dG = −SdT + VdP (1)

If P is constant, so that dP=0, then equation (1) yields

If T is constant, so that dT=0, then equation (1) yields

Differentiating equation (2) w.r.to P at constant T, yields

Differentiating equation (3) w.r.to T, at constant P yields

 It follows from equation (4) and (5) that

2 Write the four Maxwell relations?

5. What is the significance of Maxwell relations

i Using these relations tedious experimental work can be reduced into simple paper
and pencil exercise.

Maxwell relations are also very useful to deduce many other thermodynamics
relations viz. Clapeyran equation, thermodynamic equation of state etc.,

33. What is Van’t Hoff isotherm . Give its relationship?

A quantitative relationship between the free energy change and equilibrium constant is known
as Van’t Hoff isotherm.

2. Give some important significance of Van’t Hoff equation

The magnitude of the equilibrium constant also depends on whether partial pressures,
molar concentrations or mole fractions are used.
Two or more equilibria can be combined in order to get a new equilibrium.
The magnitude of the equilibrium constant depends on how the reaction is written.

3. Give the reaction between the variation of equilibrium constant with temperature.

4. The value of equilibrium constant for a reaction is found to be 10,000 at 25⁰C.

Calculate ∆G⁰ for the reaction.
We know that
∆G⁰=−RTlnK
Given:
K=10,000; T=25 + 273 = 298K; R=8.314JK-1mol-1 On substituting these value in the
above equation
∆G⁰=−RTlnK
∆G⁰=−8.314 X 298 X 2.303log10,000
=−5705.8 X 4
= −22823.2J/mole
(or) = −22823.2 X 1.987 / 8.314
−5456.6 cals.
2. Give the expressions for: a) integrated form of the Van’t Hoff equation
b) Gibbs-Helmholtz equation c) Van’t Hoff isotherm

Integrated form of Van’t Hoff equation

Gibbs-Helmholtz equation

Van’t Hoff Isotherm

PART-B

1. Derive an expression for entropy change of an ideal gas at constant temperature.

Entropy change in Isothermal expansion of an ideal gas
In isothermal expansion of an ideal gas carried out reversibly there will be no change in
internal energy i.e. ∆E = 0 and hence, from first law of thermodynamics (i.e. ∆E ═ q
+ w)
qrev = −w (1)
In such a case the workdone in the expansion of n moles of a gas from volume V1 to V2
at constant temperature T is given by

We know

P1V1 = RT; V1 = RT / P1
P2V2 = RT; V2 = RT / P2

Thus, the equation (5) is known as the entropy change of an ideal gas

2. ∆G and ∆H for a reaction at 300K are −16.0k.cal and −10.k.cal respectively.

Calculate the free energy at 330K
Solution:
The free energy change is expressed as
∆G = ∆H − T∆S ∆G = −16.0k.cals; ∆H = −10.0k.cals ; T = 300
K

The free energy at 330 K

∆G = ∆H − T∆S
∆G = −10.0 – (330 X 0.02)
= −10.0−6.6 = −16.6k.cals
3. Define Gibb’s and Helmholtz free energies. How are these two thermodynamic
functions related to the maximum and useful work obtainable from a system during
the given change.
Definition
Helmholtz Free Energy
It is known that a part of internal energy of a system can be used at constant temperature to
do some useful work. This part of internal energy (E) which is isothermally available is
called “Work Function” (A) of the system. It is mathematically defined as
A = E – TS
Significance of the Work Function (A) (or) A related to maximum work obtained
The work function is given by
A = E – TS (1)
For a small change in a reversible system at constant temperature
∆A = ∆E − T∆S (2)
But, entropy change (∆S) is given as

(or) T∆S = qrev (3)

Substituting equation (3) in equation (2), we get
∆A = ∆E – qrev (4)
But, according to first law of thermodynamics
∆E = q – w
∆E – q = −w (5)
Comparing equation (4) and (5)
∆A = −w
∆A = −wmax
−∆A = wmax
where,
wmax = maximum work

Thus,the decrease of work function (−∆A) of a process at constant temperature gives

maximum work obtainable from the system.

Gibb’s Free Energy (G) (OR) Thermodynamic Potential

Definition
A part of the total energy of the system is converted into work and the rest is unavailable.
The part of the energy which is converted into useful work is called available energy. The
isothermally available energy present in a system is called free energy (G).
It is mathematically defined as
G = H – TS

Significance of Gibbs Free Energy (G) (or) G related to useful work

Free energy (or) Gibb’s free energy (G) is the total available energy present in a reversible
system at constant temperature and pressure as useful work. It is given by
G = H – TS (1)
For a small change in a reversible system at constant temperature
∆G = ∆H − T∆S (2)
But, we know that the enthalpy change ∆H is given as
 ∆H = ∆E + P∆V (3)
Substituting equation (3) in equation (2), we get
∆G = ∆E + P∆V − T∆S (4)
But,∆A = ∆E − T∆S (or) ∆E = ∆A + T∆S
Hence, equation (4) may be written as
∆G = ∆A + P∆V (5)
Since, ∆A = −wmax
∆G = −wmax + P∆V −∆G = wmax − P∆V
where
P∆V= work done by expansion (mechanical work) wmax = maximum work that is
obtained from the system (or) wmax−P∆V = network or useful work
Hence, −∆G= wuseful
Thus, the decrease of free energy (−∆G) of a process at constant temperature and
pressure is equal to the useful work obtainable from the system.

4. Discuss the criteria for a spontaneous chemical reaction

According to the second law of thermodynamics a process is said to be spontaneous only when
∆Stotal is positive.i.e. entropy of the universe (system + surroundings) increases. This criteria of
spontaneity involves the entropy of surroundings which is difficult to measure. So, we need a
criteria which does not involve the entropy of surroundings. The change in Gibbs free energy
provides such a criteria.

We know that the total entropy change (∆Stotal) is given by

∆Stotal = ∆Ssystem + ∆Ssurrounding (1)
If a reaction is carried out at constant T and P
The amount of heat transferred by the system to surroundings is given by
∆Ssystem = (−qp)system
The amount of heat taken by the surroundings is equal to
∆Ssurrounding = (−qp)system
(qp)surroundings = −(qp)system = −∆Hsystem

Since, the surrounding is a large area, the temperature of the surroundings remains
constant, so we have

On substituting equation (2) in equation (1), we get

Multiplying the equation by T

We know ∆G = ∆H − T∆S
T∆S = ∆H − ∆G (4)
Substituting equation (4) in equation (3), we get

This equation (5) is the criterion for spontaneity interms of free energy of the system. Thus,
when ∆G = −ve (∆G<0), the process is spontaneous when ∆G = 0 , the process is in
equilibrium
when ∆G = +ve (∆G>0), the process is non-spontaneous
5. Derive Gibbs Helmholtz equation and discuss its application Gibb’s-
Helmholtz
equation (or) Relation between ∆G and ∆H
Consider the following relations
G = H – TS (Gibbs free energy)
H = E + PV (enthalpy)
Therefore, G = E + PV – TS
For infinitesimal change,
dG = dE + PdV + VdP – TdS – SdT (1)
But according to first and second law thermodynamics,
First Law , dE = dq – PdV
Second Law , dq = Tds
Therefore, dE = Tds – PdV (2)
Substituting equation (2) in equation (1) we get
dG = Tds – PdV + PdV + VdP – TdS – SdT
dG = VdP – SdT (3)
At constant pressure dP=0 and equation (3) becomes
dG = – SdT (4)

Substituting equation (5) in G = H – TS, we get

(or)

This is one form of the Gibb’s – Helmholtz equation

For any two states of the system the equation (4) may be written as
dG1 = −S1dT (Initial State)
dG2 = −S2dT (Final state)
To get the change
dG2 − dG1 = −S2dT –( −S1dT)
d(G2 – G1) = −(S2 – S1)dT
d(∆G) = −∆SdT (7)
At constant pressure the equation (7) becomes

But according to definition of free energy

∆G = ∆H − T∆S
Comparing equation (8) and (9) , we get

Similarly,

This is another form of Gibbs-Helmholtz equation

Gibb’s-Helmholtz equation relates the free energy changoe (∆G) to the enthalpy
change (∆H) and the rate of change of free energy with temperature at constant
pressure.

Applications of Gibb’s-Helmholtz Equation

1. Caluclation of Enthalpy Change (∆H) for the Cell Reaction (Galvanic
Cell)
If a cell yields nF Coulombs of electricity in a reversible manner, it must be equal to the
decrease in the free energy, then
−∆G⁰ = nFE⁰ (1)
where
n=No: of electrons involved in the process F= Faraday = 96500 Coulombs
E⁰ = Energy in volts
Hence, Gibb’s-Helmholtz equation is written as

2. Calculation of Emf of the cell

The equation (2) is divided by nF and it becomes

Calculation
3. of Entropy Change (∆S)
∆H and ∆S are related by the equation
∆G=∆H−T∆S (5)
We know that ∆G⁰=−nFE⁰
∆H can be calculated from the equation (3). Hence, ∆S can be calculated easily from the
above equation (5)
4. Gibb’s-Helmholtz equation is applicable for a process occurring at constant pressure. It is
used to calculate ∆H from the values of free energy change at two different temperature.
5. For a reaction at constant volume the equation can be modified as

6. The free energy change, ∆G for process is −138kJ at 30⁰C and −135kJ at 40⁰C.
Calculate the change in enthalpy accompanying the process at
35⁰C. Solution
According to Gibbs-Helmholtz equation

Here, ∂(∆G) = ∆G2 − ∆G1 and ∂T = T2 – T1

Given: ∆G1 = −138kJ; ∆G2 = −135kJ
T1 = 30⁰C = 30 + 273 = 303 K

T2 = 40⁰C = 40 + 273 = 313 K

The change in free energy ∆G at 35⁰C may be taken as the average value of ∆G at
30⁰C and 40⁰C

Substituting these values in the Gibbs-Helmholtz equation it becomes

= −136.5 – 308(0.3) ∆H = −228.9 kJ

7. Gibbs free energy of a reaction at 300K and 310K are −29.k.cal and −29.5k.cal
respectively. Determine its ∆H and ∆S at 300K
Solution
According to Gibbs’-Helmholtz equation

Here, ∂(∆G) = ∆G2 − ∆G1 and ∂T = T2 – T1

Given:
∆G1 = −29 k.cal (at 300 K) ∆G2 = −29.5 k.cal (at 310 K)
T 1 = 300 K ; T2 = 310 K

(i) Calculation of ∆H

∆H = −29− [ 300 X −0.05 ] = −29 + 15 = −14 k.cals.

3. Calculation of ∆S
We know that from Gibb’s-Helmholtz equation

∆S = 0.05k.cals ∆S = 0.05k.cals

8. The free energy change ∆G for a reaction is found to be −3.138 k.cal at 300 K and
for it is −14.39 cal/degree. Find ∆H for the reaction at 300
K
Solution:
According to Gibb’s Helmholtz equation

Given:
∆G = −3.138 k.cals or 3138 cals; T = 300 K

On substituting these values in the above equation

= −3138 −300(−14.39)
= −3138 + 4317
∆H = 1179 cals (or) 1.179 k.cals

7. Explain the significance of Gibbs Free Energy(G)

Free energy (or) Gibbs free energy (G) is the total available energy present in a reversible
system at constant temperature and pressure as useful work. It is given by
 G=H−TS (1)
For a small change in a reversible system at constant temperature
∆G=∆H−T∆S (2)
But we know that the enthalpy change ∆H is given as
∆H=∆E + P∆V (3)
Substituting equation (3) in (2) we get,
∆G=∆E + P∆V −T∆S (4)
But, ∆A=∆E−T∆S (or) ∆E=∆A + T∆S

Hence, equation (4) may be written as

∆G=∆A + P∆V (5)
Since, ∆A=−wmax
∆G=−wmax + P∆V (or) −∆G=wmax−P∆V
where
P∆V= work done by expansion (mechanical work) wmax = maximum work that is obtained
from the system
(or) wmax−P∆V = network or useful work Hence, −∆G= wuseful
Thus, the decrease of free energy (−∆G) of a process at constant temperature and
pressure is equal to the useful work obtainable from the system.

10. Derive all the four Maxwell relations. Thermodynamic relations(or) Maxwell
Relation
The various expressions connecting internal energy (E), enthalpy(H), Helmholtz free
energy(A) and Gibbs free energy (G) with relevant parameters such as pressure,
Temperature, volume and entropy may be given as
(i) dE = TdS – PdV
(ii) dH = TdS + VdP
(iii) dA = −SdT – PdV
(iv) dG = −SdT + VdP
From these expressions the Maxwell relations are obtained as follows.

(i) The combined form of first and second law is

dE = TdS – PdV (1)

If V is constant, so that dV= 0, then equation (1) yields

If S is constant so that dS = 0, then equation (1) yields

Differentiating equation (2) w.r.to V at constant S yields

Differentiating equation (3) w.r.to S at constant V yields

It follows from equation (4) and (5) that

Equation (6) is a Maxwell relation.

(ii) Enthalpy is defined by

H = E + PV
dH = dE + PdV + VdP but dE + PdV = TdS
 dH = TdS + VdP (7)
If P is constant so that dP═0, then equation (7) yields

If S is constant so that dS=0, then equation (7) yields

Differentiating equation (8) w.r.to P , at constant S yields

Differentiatng equation (9) w.r.to S, at constant P yields

It follows from equation (10) and (11) that

Equation (12) is also a Maxwell relation.

(iii) Helmholtz free energy (work function A) is given by

A = E−TS
dA = dE−TdS−SdT
But the combined first and second law of thermodynamics is
TdS = dE + PdV
dE = TdS−PdV
Therefore, dA = −SdT−PdV (13)

If V is constant, so that dV=0, then equation (13) yields

If T is constant so that dT=0, then equation (13) yields

Differentiating equation (14) w.r.to V, at constant T, yields

Differentiating equation (15) w.r.to T, at constat V, yields

It follows from equation (16) and (17) that

Equation (18) is also Maxwell relation

(iv) Gibbs free energy G is defined as

G = H−TS
 dG = dH−TdS−SdT
But H = E + PV
dH = dE + PdV + VdP
= TdS + VdP (since, TdS = dE + PdV)
Thus, dG = −SdT + VdP (19)
If P is constant, so that dP=0, then equation (19) yields

If T is constant, so that dT=0, then equation (19) yields

Differentiating equation (20) w.r.to P at constant T, yields

Differentiating equation (21) w.r.to T, at constant P yields

It follows from equation (22) and (23) that

Equation (24) is also Maxwell relation

Thus, equation (6),(12),(18),(24) are known as Maxwell Relations.

What is meant by Van’t Hoff isotherm? Derive an expression for the

11.
isotherm of a general reaction.
aA + bB cC + dD
VAN’T HOFF ISOTHERM
Van’t Hoff isotherm gives a quantitative relation for the free energy change and equilibrium
constant accompanying a chemical reaction. It can be derived as follows:
Consider a general reaction
aA + bB cC + dD
We know that
G = H – TS
G = E + PV – TS (Since, H = E + PV)
(or) dG = dE + PdV + VdP –TdS – SdT (1)
But dq = dE + PdV and dS = dq/T
So, the above equation (1) becomes

dG = VdP – SdT (2)

At constant temperature equation (2) becomes

dG)T = V.dP
Therefore, Free energy change for 1 mole of any gas a constant temperature is given by
dG = V.dP

On integrating equation (3) becomes

G = G⁰ + RTlnP (4) where G° = integration constant

(standard free energy change)
Let the free energies of A,B,C and D at their respective pressure PA, PB, PC and PD are GA,
GB, GC and GD respectively. Then the free energy change for the above reaction is given by
= [ cGC + dGD] − [aGA + bGB] (5)
substituting the values of GA, GB, GC and GD in equation (5) from (4), we get,
∆G = [cG⁰C + cRTlnPC + dG⁰D + dRTlnPD ] – [aG⁰A + aRTlnPA + bG⁰B + bRTlnPB ]
(or)
We know, at equilibrium, ∆G=0
∆G⁰ + RTlnKeq (7)
The equation (7) may be written as
∆G⁰ = − RTlnKeq (8) From equation (7) and (8),we get

(or)

This expression is called Van’t Hoff isotherm.

12. Derive Clapeyron-Clausius equation. Discuss its applications.

Consider a system consisting of only 1 mole of a substance existing I two phases A and B. The
free energies of the substance in two phases A and B be GA and GB. Let
the temperature and pressure of the system be T and P respectively. The system is in
equilibrium so there is no change in free energy i.e.
GA=GB (1)
If the temperature of the system may be raised to T + dT, the pressure becomes P + dP and
the free energies become GA + dGA and GB + dGB respectively. Then, the equation one
becomes
GA + dGA = GB + dGB (2)
We know that
G=H−TS (Gibss free energy)
H=E+PV (Enthalpy)
G=E+PV−TS (3)
For infinitsemal small change
dG=dE+PdV+VdP−TdS−SdT (4)
But, dE=dq−dW [ First Law of Thermodynamics]
dq=dE+PdV (5) [since, dW=PdV]
We know that for reversible equation
dq/T = dS
dq=TdS (6)
 Substituting equation (6) in equation (5)
TdS=dE + PdV
dE=TdS−PdV (7)

Substituting equation (7) in equation (4)

dG= TdS−PdV +PdV+VdP−TdS−SdT
dG= VdP−SdT (8)
Here, the work done is due to volume change only, so equation (8) may be applied to
phase A & B

dGA = VAdP−SAdT (9)

dGB = VBdP−SBdT (10)
where,
VA and VB are the molar volumes of phases A & B respectively
SA and SB are their molar entropies
Since, GA = GB hence, from equation (2)
dGA = dGB (11)
Substituting equation (9) and (10) in equation (11)
VAdP−SAdT = VBdP−SBdT (12)
SBdT−SAdT = VBdP− VAdP (13)
dT(SB−SA) = dP(VB−VA) (14)

SB−SA represents the change in entropy when 1 mole of the substance passes from the initial
phase A to the final phase B. It may be denoted as ∆S
Hence, equation (15) becomes
Substituting equation (17) in equation (16) we get,

This is the Clapeyron-clausius equation

Applications of Clapeyron-clausius equation
1. Calculation of Latent Heat of vapourization
If the vapour pressure of a liquid at two temperatures T1 and T2 be P1 and P2 respectively.
The molar heat of vapourisation ∆HV can be calculated.
2. Calculation of boiling point (or) freezing point
If the freezing point or boiling point of the liquid at one pressure is known, it is possible to
calculate it at another pressure by using Clapeyron-clausius equation.
3. Calculation of vapour pressure at another temperature
If latent heat of vapourisation is known, it is possible to calculate the vapour pressure of a liquid at
given temperature if the vapour pressure at another temperature is
known.
Calculation of molar elevation constant 4.
Molar elevation constant of a solvent can be calculated.

13. Derive an expression for the variation of equilibrium constant of a reaction with
temperature.
(OR)
(i) By combining Van’t Hoff isotherm and Gibb’s-Helmholtz equation illustrate the
effect of temperature on equilibrium constant.
(ii) What are the applications of Van’t Hoff Equation?

Variation of equilibrium constant with temperature (OR) Van’t Hoff Equation (OR) Van’t
Hoff Isochore
The effect of temperature on equilibrium constant is quantitatively given by Van’t Hoff
equation. It can be derived by combining the Van’t Hoff Isotherm with Gibb’s-Helmholtz
equation as given below.
According to the Van’t Hoff isotherm, the standard free energy change (∆G⁰) is
related to the equilibrium constant (K) by the following equation
∆G⁰ = − RTlnKP (1)
Differentiating equation (1) w.r. to temperature at constant pressure, we get

When equation (2) is multiplied by T, we get

∆G⁰ is substituted for − RTlnKP , we have

Gibb’s-Helmholtz equation for substance in their standard states may be written as

Equation (5) is introduced in equation (4)

This equation (7) is known as Van’t Hoff’s eqution.
Since, enthalpy change (∆H) does not vary appreciably with change in partial pressure of the reactants or
products, the Van’t Hoff’s equation may be written as

The equation (8) is integrated between T1 and T2 at which the equilibrium constants are K1p and K2p
respectively and ∆H is constant

This equilibrium constant K2p at temperature T2 can be calculated, if the equilibrium constant K1p at
temperature T1 is known provided the heat of the reaction (∆H) is known..
Application or Significance of Van’t Hoff Equation
1. Equilibrium constant (K) and ∆H of a reaction can be calculated using Van’t
Hoff equation.
2. A plot of logKp versus 1/T will give a straight line with slope = −∆H⁰/2.303R.
From the slope value of ∆H⁰ can be calculated. i.e. ∆H⁰ = −2.303R X slope
3. It is seen that if T2 > T1, the quantity within the square brackets is positive. (Kp)2>(Kp)1, if ∆H is a
positive quantity i.e. for an endothermic reaction the equilibrium constant increases with
remperature.
4. The magnitude of the equilibrium constant also depends on whether partial pressures, molar
concentration or mole fractions are used.
5. Two or more equilibria can be combined in order to get a new equilibrium.

6. The magnitude of the equilibrium constant depends on how the reaction is written.

14. The vapour pressure of water at 100⁰C is 760mm. What will be the vapour pressure at 95⁰C?.
The heat of vapourisation of water in this temperature range is 41.27kJ per mole.
Solution:
We know that

Given:
P2 = 760mm; T2 = 100 + 273 = 373 K P1 = ? ; T1 = 95 + 273 = 368 K
∆H = 41.27kJ/mole; R=8.314JK-1mol-1
Since, ∆H value is given in kJ, R value should be in kJ
R =( 8.314 / 1000) kJK-1mol-1 = 0.008314kJmol-1

Substituting these values in the above equation

= 2155.41 [0.0000364]
2.881 – logP1 = 0.07846
– logP1 = 0.07846 −2.881
logP1 = 2.881 – 0.07846
logP1 = 2.8025
P1 = A.log(2.8025)
P1 = 634.6 mm

The
15.equilibrium constant for the reaction N2 2NH 3 at
-4 -4
400⁰C is 1.64 X 10 and at 500⁰C is 0.144 X 10 atm. Calculate the heat of formation of 1
mole of ammonia from its elements within given range of temperature.
Solution:
We know that

Given:
K1p = 1.64 X 10-4 atm ; K2p = 0.144 X 10-4 atm T1 = 400 + 273 = 673 K; T2 = 500 + 273 = 773 K
R = 1.987 cals; ∆H = ?
Substituting these values in the above equation

−1.055 = ∆H X 4.196 X 10-5

∆H = −25143 cals ∆H = −25.143 k.cals

As per the stoichiometric equation the heat of formation of 2 mole of NH3 = −25143 cals
Therefore, heat of formation of 1 mole of NH3 = (−25143 / 2)
= −12571 cals (or) −12.571 k.cals

16. he equilibrium constant KP for the reaction, N2

2NH3 is 1.64 X 10-4 atm at 400⁰C. Calculate the equilibrium constant at 500⁰C, if ∆H = −25.140
k.cals or −105185.8 Joules ( R = 1.987 calories or 8.314 JK-1mol-1) [ 1 calorie = 4.184J]
Solution
We know that

Given:
K1p = 1.64 X 10-4 atm ; T1 = 400 + 273 = 673 K
T2 = 500 + 273 = 773 K ; ∆H = −105185.8 J
R = 8.314 JK-1mol-1 ; K2p = ?
Substituting these values in the above equation
 = −3.785 −5493.6 [ 0.0000192 ]
= −3.785 – 0.1055

K2p = A.log (−3.8905)

Therefore, the equilibrium constant at 500⁰C K2P = 1.287 X 10-4 atm
17. The equilibrium constant for a reaction at 500 and 700⁰C are 1.64 X 10-4 and 0.64 X 10 -4
respectively. Calculate the enthalpy of a reaction assuming it to be a constant over this
temperature range.
Solution
We know that

Given:
K1P = 1.64 X 10 -4 atm ; K2P = 0.64 X 10-4 atm ; T1 = 500 + 273 = 773 K T2 = 700 + 273 =
973 K; R = 8.314 JK-1mol-1
Substituting these values in the above equation

−0.409 = ∆H X 1.3888 X 10-5 ∆H = −29450 J

∆H = −29.450 kJ

UNIT IV

PHOTOCHEMISTRY AND SPECTROSCOPY

PART A

1. Define Photochemistry.
Photochemistry is the study of chemical reactions that are caused by absorption of light radiations.

What are the laws of Photochemistry?

4. The Grotthus-Draper law.
5. The Stark- Einstein law of photochemical equivalence.
6. Lamberts law.
7. Beer-Lamberts law.

3. State Grotthus – Draper law.

This law states that “when light falls on any substance, only the fraction of incident light which is
absorbed by the substance can bring about a chemical change”. It is also called the principle of
photochemical activation.

4. State Stark – Einstein law.

This law states that “In the primary photochemical process (first step) each reacting molecule is
activated by one quantum of effective light”. This law is also called the principle of quantum activation.
5. How is energy of Einstein “E” related to wavelength?
The energy E absorbed per mole of the reacting substance is given by
`E = NAhν =NAhc/λ

NA =Avagadro number = 6.023 x 1023 /mole

h = Planks constant = 6.625 x 10-34joules.sec

C = velocity of light = 3 x 108 m/sec

E = 6.023x1023/mole X 6.626 x10-34J.sec X 3x108m/sec = 0.1197 J/mol

λm λ

6. Define Beer - Lamberts law.

This law states that “When a beam of monochromatic radiation is passed through a homogenous
absorbing solution, the decrease in the intensity of the radiation dI with the thickness of the absorbing
solution dx is directly proportional to the intensity of the incident radiation I as well as the concentration
of the solution C.

λ What are the limitations of Beer-Lamberts law?

 Beer- Lamberts law is obeyed only if the radiation used is monochromatic. 
 It is applicable only for dilute solutions. 
 The temperature of the system should not be allowed to vary to a larger extent. 
  It is not applied to suspensions. 
 Deviations may contain if the solution contains impurities. 
 Deviations may also occur if the solution undergoes association or dissociation. 


λ Define Quantum yield or Quantum Efficiency.
Quantum yield (Ф) is defined as “the number of molecules of the substance undergoing
photochemical reaction per quantum of radiation absorbed‟‟. The quantum yield for photochemical
reaction is defined as
Ф = No. of molecules reacting in a given time

No. of quanta (photons) of light absorbed in the same time

9. What are the causes of high quantum yield?

 The absorption of radiation in the primary step produces atoms or free radicals, which initiates a
 series of chain reactions. 
  Formation of intermediate products which acts as catalyst. 
 The reaction is exothermic so that the heat evolved may activate other molecules which react
 without absorption of additional radiation. 
 The active molecules produced by primary absorption may collide with other molecules, thereby
activating them, which in turn further activate other reacting molecules. 

10. What are the causes of low quantum yield?
  Deactivation of the excited molecules before they form products. 
 Excited molecules may lose energy by collision with non excited molecules. 
  Molecules may receive insufficient amount of energy. 
  Primary photochemical reaction may get reversed. 
  The dissociated fragments may recombine to give reactant which results in low quantum yield. 
11. What are primary and secondary photochemical reactions?
Primary process – the reacting molecules undergo activation by absorption of light.
A+hν A*
Secondary process – the activated molecules undergo a photochemical change. A* B

12. Define Photo-Sensitization.

In some photochemical reactions, the reactant molecules do not absorb radiation and no chemical
reaction occurs. Certain reactions are made sensitive by the presence of small quantity of foreign
substance which can absorb light and stimulate the reaction without taking part in it.
The substance which absorbs light and induces a photochemical reaction without undergoing chemical
reaction is known as photosensitiser and the phenomenon is known as Photo-sensitization.

Examples:-
Atomic Photosensitisers – Mercury, cadmium, Zinc
Molecular Photosensitisers – Benzophenone, Sulphur dioxide, Uranyl sulphate.

13. What is quenching?

During Photosensitization the foreign substance (sensitizer), absorbs light and gets excited. When
the excited foreign substance collides with another substance it gets converted in to some other product
due to the transfer of its energy to the colliding substance. This process is known as quenching.

14. What is fluorescence?

Certain substances (atoms or molecules) when exposed to radiation of short wavelength (high
frequency), emit light of different frequencies compared to those of incident radiations. This process is
called fluorescence and stops as soon as the radiation is cut off. Actually decay period is very short i.e.
10-9 to 10-4 sec. The substance which exhibits fluorescence is called fluorescent substance.
Examples: - Fluorite (naturally occurring CaF2), Petroleum, Organic dyes like Eosin, fluorescein,
Chlorophyll, Quinine sulphate solution, Vapours of Sodium, Iodine, Mercury.

15. What is Phosphorescence?

Many substance (or molecules) when exposed to radiations of short wavelength (high frequency)
continue to emit light for sometime (10-4 to few seconds) even after incident light is cut off. This
phenomenon is called phosphorescence and is chiefly caused by Ultraviolet or Visible light. The
substance which exhibits phosphorescence is called phosphorescent substance. Examples: - Zinc
Sulphide, Alkaline earth sulphides (CaS, BaS, SrS).

16. Define internal conversion and intersystem crossing.

Internal conversion: - It is a type of transition which involves the return of the activated
molecule from higher excited state to the lower excited state.
S3 S2 T3 T2
S2 S1 T2 T1
 The energy of the activated molecule is dissipated in the form of heat through molecular
collisions. This process occurs in less than about 10-11 seconds. This is also known as non-radiative
transitions
Intersystem crossing: - The process in which the energy of the activated molecule is lost
through transition between states of different spin multiplicity.

S2 T2
S1 T1
Even though these transitions are forbidden they occur at relatively slow rates.

PART – B

1. Illustrate the Stark –Einstein law of Photochemical Equivalence.

This law is also called as principle of quantum activation.
This law states that “In the primary photochemical process each reacting molecule is activated by
one quantum of effective light”. This law implies a 1:1 relationship between the number of reacting
molecules and the number of quanta of light absorbed and is applicable only for the primary process.
Primary step: A+ hν A*

Secondary Step: A* B

Overall reaction: A + hν B

The molecule A absorbs a photon of light and gets activated (primary step).The activated
molecule (A*) then decomposes to yield B (secondary step).
Suppose ν is the frequency of radiation absorbed then the corresponding quantum of energy
absorbed per molecule will be hν.
The Energy absorbed per mole of the reacting substance is called one Einstein is given by `E = NAhν
=NAhc/λ

NA = Avagadro number = 6.023X 1023 /mole

h = Planks constant = 6.625X10-34 J sec
C = velocity of light = 3.08X 108 m/sec
E = 6.023x1023 X 6.626x10-34 X 3x108 = 0.1196 J/ mol
λ λ (m)
also we know 1 calorie = 4.184 J

E= 0.1196 J/mol = 2.859x10-2 cal/mol

4.184 J/cal x λ λ
2. Derive the expression for Beer – Lamberts law. State its disadvantages.
Beer-Lambert‟s law states that when a beam of monochromatic radiation is passed through a
solution of an absorbing substance, the rate of decrease of intensity of radiation (dI) with thickness of the
absorbing solution (dx) is proportional to the intensity of incident radiation, I, as well as concentration of
the solution, C.
It is mathematically represented as - dI/dx = kIC, where k = molar absorption co–efficient. Upon
integration with in the limits, we get
I x

 dI/I = - kCdx 

I0 0

ln I/I0 = - kCx or 2.303log I/I0 = - kCx log I0/I = k /2.303 * Cx

A = Cx (Beer- Lamberts law)

Where, ε = k/2.303 = molar absorptivity co–efficient. Hence, the absorbance is directly proportional to
molar concentration, C, and thickness (or) path length, x.
Application of Beer – Lambert Law
Determination of unknown concentration:
Let the absorbance and the concentration of standard solution be As and Cs, respectively, As = εCsx ……
(1),
and the absorbance and the concentration of unknown solution be Au and Cu, respectively. Au = εCux
……. (2)
Dividing equation (1) by equation (2), we get

As = Au

Cs Cu

Cu = Au * Cs

As

Thus the concentration of unknown solution is calculated.

Limitations:
  Applicable only for monochromatic light and dilute solutions. 
 Deviation occurs if the solution undergoes association or dissociation. 
 Valid only at constant temperature. 
 It is not applied to suspensions. 
 Deviations may occur if the solution contains impurities. 

3. Outline the experimental determination of quantum yield.
There are two types of determination to find out the quantum yields of photochemical reactions.
  Determination of number of moles of the light absorbing substance that react in a given time. 
 Determination of number of photons of light of required wavelength absorbed by the same
substance in the same time. 

Determination of number of moles reacting :

The number of molecules reacted in a given time can be determined by the usual analytical techniques
used in chemical kinetics.
 The rate of the reaction is measured by pipetting small quantities of sample from the reaction
mixture from time to time and the concentration of reactants are continuously measured by the usual
volumetric methods (or) change in some physical property such as refractive index / absorption / optical
rotation. From the data the amount and number of molecules reacted can be calculated.
Experimental determination of amount of photons absorbed:
A photochemical reaction takes place by the absorption of photons of light by the reacting
molecules. In order to study the rate of reaction it is essential to determine the intensity of light absorbed
by the reacting molecule.
An experimental arrangement for the study of rate of a photochemical reaction is shown in the
radiation from a suitable source (tungsten filament or mercury vapour lamp) is rendered parallel by a lens.
The parallel beam is then passed through a monochromator, which yields a beam of the desired
wavelength only. The monochromatic light then enters the reaction cell containing the reacting mixture
(made of quartz) which is immersed in a thermostat. Finally, the light transmitted from the cell is made to
fall on a detector which measures the intensity of the transmitted radiation.
The intensity of radiation is generally measured with the help of actinometer. It contains 0.05 M oxalic
acid and 0.01 M uranyl sulphate in water.
On exposure to radiation the following reaction takes place.
UO22+ + hν (UO22+)*

UO22+ + COOH CO2 + CO + H2O + UO22+

COOH

The standard solution of uranyl oxalate is exposed to light radiation of definite frequency for a certain
period of time. The extent of reaction can be determined by titrating the remaining oxalic acid with standard
KMnO4 solution. The amount of oxalic acid consumed in the photochemical reaction is a measure of intensity
of radiation (i.e. number of photons absorbed).

3. Explain the mechanism of photochemical decomposition of HI. Comment on the reason for low
quantum yield.
The photochemical decomposition of HI is found to take place in the wavelength range of 2070Å -
2820Å.The following mechanism has been suggested for the photochemical decomposition of HI.
One molecule of HI absorbs one quantum of radiation (primary process)
HI + hν k1 H+I Rate = k1Iabs

H + HI k2 H2 + I Rate = k2 [H] [HI]

I+I k3 I2 Rate = k3 [I]2
The overall rate of decomposition of HI is given by adding the rate equation (i) & (ii) -d[HI] =
k1Iabs + k2 [H] [HI] (1)

dt

Applying steady state approximation to [H] ,we have

d [H] = k1Iabs - k2 [H] [HI] =0

dt

k1Iabs = k2 [H] [HI] (2)

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

-d[HI] = k1Iabs + k1Iabs = 2 k1Iabs
 dt

The quantum yield of the reaction is given by

Ф = Rate of disappearance of HI = -d [HI]/ dt = 2 k1Iabs = 2.0

Rate of absorption of light k1Iabs k1Iabs
Actually the quantum yield of the reaction falls below 2.0 after sometime. This is due to the fact
that sufficient I2 is produced in step (iii), the following reaction, regenerating, HI is also set up. H + I2
HI + I

4. Explain the mechanism of photo physical process with the help of Jablonski diagram.
Spin multiplicity:-Most molecules posses an even number of paired electrons in ground state. The spin
multiplicity of the state is given as 2S + 1, where S is the total spins of the electrons When the spins are
paired
Then S = s1+ s2 = +1/2 + (-1/2) = 0

Hence 2S + 1 = 2x0 + 1 =1, the spin multiplicity is 1.

The molecule is in singlet ground state.

Spin Orientation due to absorption of light

On absorption of a photon of energy hν, one of the paired electrons goes to a higher energy level (i.e.
excited state). The spin orientation of the two electrons may be either parallel or antiparallel. If the spins
are parallel, then
S = s1+ s2 = +1/2 + (+1/2) = 1
Hence 2S + 1= 2x1 +1 =3, the spin multiplicity is 3. The molecule is in triplet excited state.
If the spins are antiparallel, then
S = s1+ s2 = +1/2 + (-1/2) = 0
Hence 2S+ 1= 2x 0+ 1 = 1, the spin multiplicity is 1.
The molecule is in singlet excited state. Depending upon the energy hυ of a photon, electron can jump to
any higher electronic state and hence we get a series of
Singlet excited states S1, S2, S3, Triplet excited state T1, T2, T3…
S1, S2, S3… etc is called first singlet excited state, second singlet excited state, and third singlet excited
state respectively.
T1, T2, T3… etc is called first triplet excited state, second triplet excited state, and third triplet excited
state respectively.
According to Quantum mechanics the singlet excited state has higher energy than corresponding
triplet excited state. Thus E (S1) > E (T1); E (S2) > E (T2) ; E(S3) > E(T3)
Consequences of light absorption: When light photon (hν) is absorbed by a molecule, the electron of the absorbing
molecule may jump from S0 (Singlet ground state) to singlet excited state S1 or S2
or S3.
Depending upon the energy of the light photon absorbed, for each singlet excited state (S1, S2, S3 etc)
there is a corresponding triplet state respectively. (T1, T2, T3etc).The molecule is said to be activated,
whether it is in singlet excited state or triplet excited state.
M0 + hν M*
M0 = Molecule in the ground state M*=Molecule in the activated state.
The activated molecule returns to the ground state by dissipating its energy (hν) through any of the
following type of process.
1.Non-radiative transitions:-Such a transition is from the higher excited states (S1, S3 or T2, T3) to the
first excited state (S1 or T1).Since such a transition does not involve the emission of radiation, it is
referred to as radiation less or non radiative transitions.
2. Internal Conversion: - These transitions involve the return of the activated molecule from the higher
excited state to the first excited states. The energy of the activated molecule is dissipated in the form of
heat through molecular collisions.
This process occurs in less than about 10-11s
S3 S1 T3 T1
S2 S1 T2 T1
Inter system crossing: - (ISC)
The process in which the energy of the activated molecule is lost through transition between state of
different spin multiplicity. Even though these transitions are forbidden, they occur at relatively slow rates
S2 T2
S1 T1
Radiative transition:-
These transitions involve the return of the activated molecule from the singlet excited state S1 and the
triplet excited state T1 to the singlet ground state S0. So, such a transition is accompanied by emission of
radiation.
When a molecule in the S1 state returns to the ground state S0, emission of radiation occurs in about 10-
8
s and this process is known as fluorescence.
When a molecule in the T1 state returns to the ground state S0, emission of radiation occurs at a rather
slow rate. This process is called phosphorescence. Since the T1 to S1, transition is spectroscopically
forbidden the life time of phosphorescence is much longer (about 10-3 and higher).

6. Explain the mechanism of energy transfer in photochemical reactions. Photosensitization and

Quenching:-
In some photochemical reactions, the reactant molecules do not absorb radiation and no chemical reaction
occurs. Certain reactions are made sensitive by the presence of small quantities of foreign substance which
can absorb light and stimulate the reaction without taking part in it. The substance which absorbs light and
induces a photochemical reaction without undergoing chemical reaction is known as photosensitiser and
the phenomenon is known as Photo-sensitization.

Examples:-
Atomic Photosensitisers – Mercury, cadmium, Zinc
Molecular Photosensitisers – Benzophenone, Sulphur dioxide, Uranyl sulphate.
During Photosensitization the foreign substance (sensitizer), absorbs light and gets excited. When the
excited foreign substance collides with another substance it gets converted in to some other product due to
the transfer of its energy to the colliding substance. This process is known as quenching.
Mechanism of photosensitization and Quenching:-
Consider a general donor – acceptor system in which only the donor D i.e. the sensitizer, absorbs
the incident photon and the triplet state of the donor is higher than the triplet state of the acceptor A .i.e.
the reactant. Absorption of the photon produces the singlet excited state of the donor,1D which via
intersystem crossing (ISC) gives the triplet state of the donor 3D. This triplet excited state then collides
with the acceptor producing the triplet excited state of the acceptor 3A and the ground state of the donor.
If 3A gives the desired product, the mechanism is called photosensitization.
However if the desired products result from the excited state of the donor (3D), then A is called the
quencher and the process is known as quenching.
The reactions for photosensitization and quenching may be represented as below,
D + hν 1D

1D 3D
 3
D+A D + 3A
3
A products (photosensitization)
3D products (quenching)
The triplet excited state of the sensitizer or donor 1D must be higher in energy level than the triplet excited
state of the reactant or acceptor (3A) so that the energy available is enough to raise the reactant molecule
to its triplet state.

Examples of photosensitized reactions:-Dissociation of H2 molecule:

Irradiation of a mixture of hydrogen gas and mercury vapour with light of wavelength 253.7 nm
brings about dissociation of hydrogen molecule in to hydrogen atom.
Hg + hν Hg*
Hg* + hν H2* + Hg
H2* 2H
Here mercury acts as photosensitiser.
Photosynthesis in plants:-
The most outstanding example for photosensitization is photosynthesis of carbohydrates in plants
from H2O and CO2in which the green colouring matter of plants acts as photosensitiser. CO2 and H2O do
not absorb any radiation in the visible region, but chlorophyll absorbs the radiation. It absorbs visible light
in the wavelength range of 400-700 nm. The energy of light absorbed by chlorophyll is transferred to CO2
and H2O which then react to form (CH2O) n (cellulose /sugar).

6. Explain the mechanism of chemiluminescence with examples.

Chemiluminescence is defined as the production of light by a chemical reaction and is thus the reverse
of photochemical reaction. In order for a reaction to be chemiluminescent it must furnish sufficient energy
to raise at least one of the reactants or intermediates to an electronically excited state so that as it returns to
the ground state, it emits energy in the form of radiation.
Since the emission occurs at ordinary temperature, the emitted radiation is also known as “cold light”.
Examples of chemiluminescence reactions:
v) The glow of phosphorus and its oxide, in which the oxide in its electronic excited state emits radiation.
vi) Oxidation of 5-mainophthalic hydrazines or cyclic hydrazines by H2O2 emits green light. 3.‟Cold
light‟ emission by glow worms. This is an example of bioluminescence due to aerial oxidation of
luciferon (a protein) in the presence of enzyme (luciferase).

SPECTROSCOPY
PART A
1) How does molecular spectrum arise?
Molecular spectrum arises due to the interaction of electromagnetic radiation with molecule.

2.What are the differences between atomic spectra and molecular spectra?
Atomic Spectra Molecular Spectra
Interaction of electromagnetic radiation Interaction of electromagnetic radiation with
with atoms. molecules.
Line spectrum is obtained Complicated spectrum is obtained
It is due to electronic transition in an It is due to vibrational, rotational and
element. electronic transition in a molecule.

3. Calculate the number of modes of (IR) vibration for the following molecules.
 For a molecule contain N atoms, the number of vibration modes are given by:
(a) CH4 (Non linear molecule) = 3N- 6 = (3 x 5) – 6 =9
(b) CO2 (linear molecule) = 3N- 5 = (3 x 3) – 5 = 4
(c) C2H6 (Non linear molecule) = 3N- 6 = (3 x 12) – 6 = 30
(d) HCl (linear molecule) = 3N- 5 = (3 x 2) – 5 =1

4. What is Finger Print region? Mention its uses.

The vibration spectral region at 1400 – 700 cm -1 gives very rich and intense absorption bands which is
unique for each molecule. This region is termed as Finger Print Region.
Uses: It can be used to detect the presence of functional group and also to identify and characterize the
molecule just as a finger print can be used to identify a person.

5. What are the differences between Chromophore and Auxochrome?

S.No Chromophore Auxochrome
1. This group is responsible for the It does not impart colour, but when
colour of the compound. conjugated with a chromophore colour
is produced.
2. It does not form salt. It forms salt.
3. It contains at least one multiple It contains lone pair of electrons.
bond.
eg: -NO2, -NO , -N=N- eg: -OH , -NH2 , -NR2

6. Mention three applications of UV-Visible Spectroscopy.

i. Quantitative analysis: By using Beer-Lamberts law, the concentration of unknown solution can be
determined.
1. Qualitative analysis: It is used for identification of aromatic compounds and conjugated olefins.
2. Detection of impurities: It is used for detecting impurities in organic compound

7. Name the transition responsible for molecular spectra.

The molecular spectrum arises due to the following three transitions. Rotational transitions
Vibrational transitions Electronic transitions.

8. What is the relation between wavelength, frequency and wave number?

1/λ = υ = υ/c
1. What are the factors which affect the absorbance of the photons by a molecule?
The nature of the absorbing molecules
The concentration of the molecules
Path length of radiation
75

10. Define the term – Bathochromic shift, Hypsochromic shift

Bathochromic shift: shifting of absorption band towards a longer wavelength. Hypsochromic shift:
shifting of absorption band towards a shorter wavelength.

PART B

1. What is principle of UV Spectroscopy? Explain its components and working. Principle:

UV – Visible spectra arises from the transition of valence electrons from the ground state to
excited state by absorbing light from UV (100 – 400 nm) or visible region (400 – 750nm). It is a type of
absorption spectra.
Components:
Radiation source: Hydrogen or Deuterium lamps are radiation source for UV region and tungsten
filament lamp for visible region.
Monochromators: The monochromators is used to select a particular wavelength.
Cells: The cells are made up of quartz glass are used to hold the sample which should fulfill the following
conditions.
They must be uniform in construction. The material should be inert to solvents.
They must be transparent to UV and Visible light.
Detectors: The converts the radiation in to current which is directly proportional to the concentration of
the solution
Eg.. They are Photo multiplier tube or Photocells.
Recorder: The recorder records the signal from the detector and shows a display.
Working:
The Radiation from the source is allowed to pass through the monochromator. It allow particular
wavelength of light to pass through the exit slit. The beam of radiation coming out of the slit is split into
two parallel beams.
One half of the beam passes through the sample cell and another half passes through reference cell (only
solvent). The detectors compare the intensities of the transmitted two beams of light. If the compound
absorb light at a particular wavelength, the intensity of the transmitted beam through sample (I) will be
less than that of reference beam (Io). The recorder produces the graph,

which is a plot of wavelength of light Vs absorbance of light. This graph is known as adsorption spectrum.
8. Explain the principle, components and working of IR spectroscopy.
Principle:
IR Spectra is produced by the absorption of energy by a molecule in the infrared region and the
transitions occur between vibrational levels.
Range of IR radiation:
Near Infrared 12500= – 4000 cm-1
Infrared 4000= – 667 cm-1
Far Infrared 667 =– 50 cm-1
Components:
Radiation source: The main source of radiation is Nichrome wire or Nernst glower which is a filament
containing oxides of Zr, Th, Ce held together with a binder.
Monochromators: It allows the light of the required wavelength to pass through light of other Sample
cell: The cells must be transparent to IR radiation are used to hold the sample. Detector: Detectors are
used to convert thermal radiant energy into electrical energy. Recorder: The recorder record the signal
coming out from the detector
Working:
The radiation emitted by the source is split into two parallel beams. One of the beams passes through the
sample and the other passes through the reference sample. When the two beams of light recombine they
produce a signal which is measured by detector. The signal from the detector is recorded by the recorder.

9. Explain the molecular vibration in IR spectrum. Calculate the fundamental modes of vibration
for non-linear and linear molecule.
There are two kinds of fundamental vibrations in molecule.
Stretching vibrations: During stretching, the distance between two atoms decreases or increases, but
bond angle remains unaltered.
Bending vibrations: During bending, bond angle increases or decreases but bond distance remains
unaltered.
Types of Stretching and bending vibrations
The number of fundamental modes of vibration of a molecule can be calculated as follows. Non-linear
molecule has 3N-6fundamental modes of „vibrations and a linear molecule has 3N-5 fundamental modes
of vibrations where N is the number of atoms in a molecule..
Stretching vibrations: It classified into two types
(i) Symmetric stretching: The atoms of the molecule are moving in the same direction. (ii) Asymmetric
stretching: The atoms of the molecule are moving in opposite direction.
Asymmetric stretching requires more energy than the Symmetric stretching. Bending vibrations: It
classified into two types.
In-plane bending Out-of plane bending
Fundamental modes of vibration for non-linear and linear molecule
Methane1. (CH4) (N=5)
It is a non-linear molecule. Hence, 3N-6 = 3x5-6 = 9 Fundamental vibrational modes.
Benzene2.(C6H6) (N=12)
It is a non-linear molecule. Hence, 3N-6 = 3x12-6 = 30 Fundamental vibrational modes.
2. Water (H2O) (N=3) It is a non-linear molecule. Hence, 3N-6 = 3x9-6 = 3 Fundamental vibrational
modes.
(i) Symmetric stretching (ii) Asymmetric stretching (ii) Bending vibration

υ1 = 3652 cm-1 υ2 = 3756 cm-1 υ1 = 1596 cm-1

4. Carbon dioxide (CO2) (N=3)

It is a linear molecule. Hence, 3N-5 = 3x3-5 = 4 Fundamental vibrational modes.

(i) (ii) (iii) (iv)

Symmetric stretching Asymmetric stretching In-plane Bending Out-plane bending

υ1 = 1340 cm-1 υ2 = 2350 cm-1 υ3 = 666 cm-1 υ4 -1

666 cm =

10. Discuss the applications of UV-Spectroscopy.

Qualitative analysis: Many types of compounds can be identified by comparing the UV spectrum of the
sample with that of similar compounds available in reference books. Testing the purity of the sample:
UV Visible spectroscopy is the best method for detecting impurities in organic compounds because
  The bands due to impurities are very intense. 
 Saturated compounds have weak absorption band and unsaturated compounds have strong
absorption band. 
The kinetics of chemical reaction: The progress of a chemical reaction can be easily followed by
examining the UV-spectra of test solution at different time intervals. The concentration of either the
reactant or product can be followed.

Determination of calcium in blood serum. Calcium in blood serum in indirectly determined by

converting the Ca present in 1 ml of serum as calcium oxalate, and dissolving the calcium oxalate in dilute
sulphuric acid and treated with ceric sulphate solution. The absorption of the excess Ce+4ion is measured
at 315nm. The amount of Ca in blood serum is indirectly calculated from the amount of Ce+4ion
consumed by the calcium oxalate.
Quantitative analysis: UV absorption spectroscopy is used for the quantitative determination of
compounds based on Beer-Lambert‟s law.

11. Discuss the applications of IR spectroscopy.

 Identification of organic compounds. : IR spectroscopy is very useful in identification of organic
compounds.
Identification of functional groups: The region from 4000 – 1400 cm-1 in IR spectrum is useful for
functional group analysis.

Group Frequency range

C=O 1750 – 1600 cm-1
Free OH 3650 – 3300 cm-1
H bonded OH 3300 – 2800 cm-1
-C = C- 2250 – 2100 cm-1
-C = N 2260 cm-1
-NH2 3350 cm-1
-N = O 1600 – 1500 cm-1
-COOH 3300 – 2700 cm-1

Testing the purity of a sample: Presence of an impurity can be detected by their characteristic peaks.
Determination of symmetry of a molecule: The symmetry of a molecule whether linear or non-linear can
be determined from the IR spectrum.
Example: IR spectra of H2O gives 3 peaks at 667 cm-1, 1330cm-1, 2349 cm-1. Since non-linear molecule
should exhibit (3N-6) = 3 peaks, the compound is non linear.
Study of hydrogen bonding molecule: Intermolecular and Intramolecular hydrogen bonding can be
differentiated by taking a series of spectra of a compound at different concentrations. Intermolecular
hydrogen bonding decreases with dilution and the intensity of such peaks will also decrease.
Intramolecular hydrogen bonding on the other hand will show no such change. This can be explained by
taking the ortho and para nitrophenols.
Study of progress of a chemical reaction
The rate the reaction can be determined by taking IR spectra at regular intervals of time Example:
Oxidation of secondary alcohol to ketone
Secondary alcohol gives the absorption band at 3570cm-1 due to - OH stretching slowly disappears and a
new band appears at 1725cm-1 due to C=O stretching.

12. What are the different types of electronic transactions? Draw the energy level diagram for
various transitions.
n→π* transitions:
n→π* transitions are shown by unsaturated molecule containing hetero atoms like N, O & S.
It occurs due to the transition of non-bonding lone pair of electrons to the antibonding

orbitals.This transition shows a weak band, and occurs in longer wavelength with low intensity. Example
aldehyde & ketone with no double bond shows a band in the range of 270-300nm and if it is existing with
the double bond show a band in the range of 300-350nm.
n→π* transitions:
n→π* transitions are shown by unsaturated molecule containing hetero atoms like N, O
& S. It occurs due to the transition of non-bonding lone pair of electrons to the antibonding orbitals.This
transition shows a weak band, and occurs in longer wavelength with low intensity. Example aldehyde and
ketone with no double bond shows a band in the range of 270-300nm and if it is existing with the double bond
show a band in the range of 300-350nm.
σ→σ* transitions:
This type of transitions occurs in the compounds having only single bonds. Energy required for
this transition is more and absorption band occurs in the far UV region (120-136 nm) Example: Methane,
Ethane
n→σ* transitions:
 These transitions occur in saturated compounds having lone pair of electrons. This transition
occurs along with n→σ* transition .The energy required for this transition is less than σ→σ* so absorption
band occurs at longer wavelength in the near UV region (180-200nm). Example: (CH3)3N for n→σ*
transition- at 227nm, for σ→σ* transition at 99nm.
π→π* transitions:
These transitions occur in unsaturated compounds i.e. the compounds having
double bond and triple bonds. Example: Ethylene molecule shows intense band at 174nm and weak band
at 200nm. Both are due to π→π* transitions. According to selection rule, the intense band at 174nm is due
to allowed transistion.If there is any alkyl substitution in olefins shifts the absorption band to longer
wavelength. This effect is known is batho-chromic effect or red shift.

UNIT IV
PHASE RULE AND ALLOYS
Chemical reactions are of two types
1. Irreversible reaction homogeneous
2. Reversible reaction – it’s of two types
A. homogeneous reversible reaction heterogeneous
B.heterogeneous reversible reaction --- its behaviour can be studied by PHASE RULE given by
Willard Gibbs (1874).
Phase rule
The number of degree of freedom (F) of the system is related to number of components (C) and number
of phases (P) by the following phase rule equation.
F = C-P+2
Explanation or meaning of terms 1. Phase (P)
Any homogeneous physically distinct and mechanically separable portion of a system which is separated
from other parts of the system by definite boundaries.
Gaseous phase
All gases are completely miscible and there is no boundary between one gas and the other. For
example: air – single phase
b.Liquid phase
It depends on the number of liquids present and their miscibilities.
8. If two liquids are immiscible, they will form three separate phases two liquid phase and one
vapour phase. For example: benzene-water.
9. If tow liquids are miscible, they will form one liquid phase and one vapour phase. For example:
alcohol – water.
C .Solid phase
Every solid constitutes a separate phase
For example:
(i) Water system ------- three phases
(ii) Rhombic sulphur (s) monoclinic sulphur
----- two
(s) phase
iii) Sugar solution in water ----- one phase
iv) CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(g) ---- three phases.
2. Component (C)
“The smallest number of independently variable constituents, by means of which the
composition of each phase can be expressed in the form of a chemical equation”.
For example:
i) Water system ---- one component ( H2O )
ii) An aqueous system of NaCl --- two component ( NaCl , H2O )
iii) PCl5(s) PCl3 (l) + Cl2 (g) two component
--- ,three phases
λ CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(g) ---- three phases,two

component
3. Degree of freedom(F)
 “The minimum number of independent variable factors such as temperature, pressure and
concentration, which much be fixed in order to define the system completely”.

i) Water system

Ice (s) water (l) vapour (g)

F = Non variant (or) zero variant
ii) Ice (s) water (l)
F = univariant (one)
iii) For a gaseous mixture of N2 and H2, we must state both the pressure and temperature.
Hence,the system is bivariant.
PHASE DIAGRAM:
Phase diagram is a graph obtained by plotting one degree of freedom against another.
Types of phase diagrams
(i)P-T Diagram : used for one component system
(ii) T-C Diagram : used for two component system
APPLICATIONS OF PHASE RULE TO ONE COMPONENT SYSTEM The water system:
Water exists in three possible phases namely solid, liquid and vapour. Hence there
can be three forms of equilibria.
Solid Liquid
Liquid Vapour
Solid Vapour
Each of the above equilibrium involves two phases. The phase diagram for the water system is shown in
the figure.
This phase diagram contains curves, areas, and triple.

(i)Curve OA
The curve OA is called vaporisation curve, it represents the equilibrium between water and
vapour. At any point on the curve the following equilibrium will exist.
Water Water vapour
The degree of freedom of the system is one, i.e, univariant.
This is predicted by the phase rule.
F=C-P+2; F=1-2+2; F=1
This equilibrium (i.e. Line OA) will extend up to the critical temperature (347o C). Beyond the critical
temperature the equilibrium will disappear only water vapour will exist.
(ii) Curve OB
The curve OB is called sublimation curve of ice, it represents the equilibrium between ice and
vapour. At any point on the curve the following equilibrium will exist.
ICE VAPOUR
The degree of freedom of the system is one, i.e. univariant. This is predicted by the phase rule.
F = C – P + 2; F = 1-2=2 ; F=1
This equilibrium (line OB) will extend up to the absolute zero (-273o C), where no vapour can be present
and only ice will exist.
iii) Curve OC
The curve OC is called melting point curve of ice, it represents the equilibrium between the ice and water.
At any point on the curve the following equilibrium will exist.
Ice water
The curve OC is slightly inclined towards pressure axis. This shows that melting point of ice
decreases with increase of pressure.
The degree of freedom of the system is one i.e., univariant. iv) point O (triple point)
The three curves OA ,OB ,OC meet at a point “O” ,where three phases namely solid ,liquid and vapour
are simultaneously at equilibrium .
This point is called triple point, at this point the following equilibrium will exist.
Ice water vapour
The degree of freedom of the system is zero i.e., nonvariant.This is predicted by the phase rule. F=C-
P+2; F=1-3+2=0
Temperature and pressure at the point “O” are 0.0075 oC and 4.58 mm respectively.
(v) Curve OB’: Metastable equilibrium
The curve OB’ is called vapour pressure curve of the super-cool water or metastable equilibrium where
the following equilibrium will exist.
Super-cool water vapour
Sometimes water can be cooled below O oC without the formation of ice, this water is called super –
cooled water. Super cooled water is unstable and it can be converted in to solid by seeding or by slight
disturbance.
vi) Areas
Area AOC, BOC, AOB represents water, ice and vapour respectively .The degree of the freedom of the
system is two.i.e. Bivariant.
This is predicted by the phase rule
F=C-P=2; F=1-1+2; F=2
Two component alloy system or multi component equilibria Reduced phase rule or condensed
system
The system in which only the solid and liquid are considered and the gas phase is ignored
is called a condensed system.since pressure kept constant, the phase rule becomes
F’ = C – P + 1
This equation is called reduced phase rule.
Classification of two component system

Based on the solubility and reactive ablity, the two component systems are classified in to three types.

4. Simple eutectic formation - A binary system consisting of two substances, which are completely
miscible in the liquid state, but completely immiscible in the solid state, is known as eutectic (easy melt)
system. They do not react chemically. Of the different mixtures of the two substances, the mixture having
the lowest melting point is known as the eutectic mixture.

5. a) formation of compound with congruent melting point

6. Formation of compound with incongruent melting point
Formation of solid solution

BINARY ALLOY SYSTEM OR THE SIMPLE EUTECTIC SYSTEM The Lead – Sliver system
Since the system is studied at constant pressure,the vapour phase is ignorned and the
condensed phase rule is rule is used.
F I= C-P+1
The phase diagram of lead –sliver system is shown in the figure It contains lines,areas and the
eutectic point.
i) curve AO
The curve AO is known as freezing point curve of sliver.
Along the curve AO, solid Ag and the melt are in equilibrium.
Solid Ag melt
According to reduced phase rule
F’=C-P+1
C=2
P=2
F’=1
The system is univariant
ii) curve BO
The curve BO is known as freezing point curve of lead .
Along the curve BO, solid Pb and the melt are in equilibrium.
Solid Pb melt
According to reduced phase rule
F’=C-P+1
C=2
P=2
F’=1
The system is univariant.
v) Point “ O ” (eutectic point)
The curves AO and BO meet at point ‘ O ‘ at a temperature of 303 o
C ,where the three
phases are in equilibrium.

Solid Pb + soild Ag melt

According to reduced phase rule
F’=C-P+1
C=2
P=3
F’=1
The system is non-variant.

The point “ O “ is called eutectic point or eutectic temperature and is corresponding

composition,97.4 % Pb and 2.6 % Ag ,is called eutectic composition.below this point
the eutectic compound and the metal solidfy.
vii) Areas
The area above the line AOB has a single phase( molten Pb + Ag ). According to
reduced phase rule
F’=C-P+1 C=2
P=1
F’=2
The system is bi-variant.
The area below the line AO ,OB and point “O” have two phases and hence the system
is univariant.
According to reduced phase rule F’=C-P+1
C=2
P=2
F’=1
The system is uni-variant.
The process of raising the relative proportion of Ag in the alloy is known as pattinson’s process.
The Pattinson process was patented in 1833. It depended on well-known material properties;
essentially that lead and silver melt at different temperatures. The equipment consisted of a row of about
8-9 iron pots, which could be heated from below. Agentiferous lead was charged to the central pot and
melted. This was then allowed to cool, as the lead solidified, it was skimmed off and moved to the next
pot in one direction, and the remaining metal was then transferred to the next pot in the opposite
direction. The process was repeated in the pots successively, and resulted in lead accumulating in the
pot at one end and silver in that at the other. The process was economic for lead containing at least 250
grams of silver per ton.
Uses of eutectic system
1.suitable alloy composition can be predicted with the help of eutectic systems.
2.eutectic systems are used in preparing solders ,used for joining two metal pieces
together.
Melting point
It is the temperature at which the solid and liquid phases, having the same composition ,are in
equilibrium.
Solid A solid B

Eutectic point
It is the temperature at which two solids and a liquid phase are in equilibrium .
Solid A + solid B Liquid
Triple point
It is the temperature at which three phases are in equilibrium.
Solid liquid vapour
By definition ,
All the eutectic points are melting points, but all the melting points need not be eutectic points. ll ly , all the
eutectic points are triple points ,but all the triple points need not be eutectic points.
Uses (or) merits of phase rule
1. It is a convenient method of classifying the equilibrium states in terms of phases ,components and
degree of freedom.
2. It helps in deciding whether the given number of substances remain in equilibrium or not.
Limitations of phase rule
1.phase rule can be applied for the systems in equilibrium.
2.only three variables like P,T & C are considered ,but not electrical, magnetic and gravitational forces.
ALLOYS
Definition
An alloy is defined as “homogeneous solid solution of two or more different element one of
which at least is essentially a metal”. Alloy containing Hg as a constituent element are called
amalgams.
Properties of alloys
2) Alloy are harder less malleable and possess lower melting point than their component
metals
3) Alloys possess low electrical conductivity
4) Alloys resist corrosion and the action of acids
Importance or need of making alloys
3. To increase the hardness of the metal Example
Gold and silver are soft metal they are alloyed with copper to make them hard
2. To lower the melting points of the metal Example
Wood metal (an alloy of lead, bismuth, tin and cadmium) melts at 60.5⁰c which is
far below the melting points of any of these constituent metals
3. To resist the corrosion of the metal
 Example

Pure iron rested but when it is alloyed with carbon chromium (stainless steel) which
resists corrosion
4. To modify chemical activity of the metal
Example
Sodium amalgam is less active than sodium but aluminium amalgam is more active
than aluminium
5. To modify the colour of the metal Example
Brass an alloy of copper (red) and size (silver-white) is white colour.
6. To get good casting of metal Example
An alloy of lead with 5% tin and 2% antimony is used fro casting printing type due
toits good casting property
Functions (or) effects of alloying elements
Addition of small amount of certain metals such as Ni, Cr, Mo, Mn, Si, v and Al impart
special properties like hardness, tensile strength, resistance to corrosion and coefficient of
expansion on steel. Such products are known as special steel or alloy steels
Some important alloying element and their functions are given in table

CLASSIFICATION (OR) TYPES OF ALLOYS

ALLOYS

FERROUS ALLOYS NON-FERROUS ALLOYS

(i)Nichrome
(i) Solder
(ii) Alnico
(ii) Brass
(iii)Stainless steel
(iii) Bronze
FERROUS ALLOYS OR ALLOY STEELS
Ferrous alloys are the type of steels in which the elements like Al,B,Cr,Co,Cu,Mn are present in
sufficient quantities, in addition to carbon & iron.
PROPERTIES
2. High yield point & strength
3. Sufficient formability,ductility & weldability
4. Corrosion & abrasion resistant
5. Less distortion & cracking
6. High temperature strength
IMPORTANT FERROUS ALLOYS (i)NICHROME
Nichrome is an alloy of nickel & chromium
COMPOSITION
Nickel – 60% Chromium – 12% Iron – 26%

Manganese – 2%
PROPERTIES
3. Good resistance to oxidation & heat
4. High melting point & electrical resistance
5. Withstand heat up to 1000-1100⁰C
USES
1. Used for making resistance coils,heting elements in stoves & electric irons
 2. Used in making parts of boilers,steam lines stills,gas turbines,aero engine
valves,retorts,annealing boxes.
(ii)ALNICO
Alnico is an alloy of aluminium-nickel-cobalt .
COMPOSITION
Aluminium – 8-12% Nickel – 14-28% Cobalt – 5-35%
PROPERTIES
1. Excellent magnetic properties & high melting point
2. Magnetized to produce strong magnetic fields as high as 1500 gauss
TYPES OF ALNICO ALLOYS
Alnico alloys are of two types
1. ISOTROPIC ALNICO
It is effectively magnetized in any direction
2.ANISOTROPIC ALNICO
It possess preffered direction of magnetization.
Anisotropic alnico possesses greater magnetic capacity in their preffered
orientation than isotropic alnico.
USES

2. Used as permanent magnets in motors,generators,radio speakers microphones,telephone

receivers & galvanometers.
(iii)STAINLESS STEELS (or)CORROSIOPN RESISTANT STEELS
 These are alloy steels containing chromium together with other elements such as
nickel,molybdenum,etc. 
 Chromium-16% or more 
 Carbon-0.3-1.5% 
PROPERTIES
1. Resist corrosion by atmospheric gases & also by other chemicals.
2. Protection against corrosion is due to the formation of dense, non-porous,tough
film of chromium oxide at the metal surface. If the film cracks, it gets automatically
healed up by atmospheric oxygen

1. HEAT TREATABLE STAINLESS

STEEL COMPOSITION
Carbon-1.2% Chromium-less than 12-16%
PROPERTIES
Magnetic,tough & can be worked in cold condition

USES
1. Can be used up to 800⁰C
2. Good resistant towards weather & water
4. In making surgical instruments,scissors,blades,etc.
2.HEAT TREATABLE STAINLESS STEEL PROPERTIES
 Possess less strength at high temperature 
 Resistant to corrosion 
TYPES OF NON HEAT TREATABLE STAINLESS STEEL
(a)MAGNETIC TYPE
COMPOSITION
Chromium-12-22%
Carbon-0.35%
PROPERTIES
1. Can be forged,rolled & machined
2. Resist corrosion
USES
Used in making chemical equipments& automobile parts.
(b)NON MAGNETIC TYPE COMPOSITION
Chromium-18-26% Nickel-8-21% Carbon-0.15%

Total % of Cr & Ni is more than 23%. EXAMPLE:18/8 STAINLESS STEEL COMPOSITION:

Chromium-18%
Nickel-8%
PROPERTIES
1. Resistance to corrosion.
2. Corrosion resistance is increased by adding molybdenum

USES
In making household utensils,sinks,dental & surgical instruments.
NON FERROUS ALLOYS
 Do not contain iron as one of the main constituent. 
 Main constituents are copper,aluminium,lead,tin,etc. 
PROPERTIES

1. Softness & good formability

2. Attractive (or) very good colours
3. Good electrical & magnetic properties
4. Low density & coefficient of friction
5. Corrosion resistance
IMPORTANT NON FERROUS ALLOYS 1. COPPER ALLOYS (BRASS)
Brass contains mainly copper & zinc
PROPERTIES
 Greater strength, durability & machinability 
 Lower melting points than Cu & Zn 
 Good corrosion resistance & water resistance property 
2.BRONZE(COPPER ALLOY) 
Bronze contains copper & tin
PROPERTIES
 Lower melting point 
 Better heat & electrical conducting property 
 Non-oxidizing,corrosion resistance & water resistance property. 
3.SOLDERS 
Solders are low- melting alloys of tin & lead
PROPERTIES
Solder is melted to join metallic surfaces ,especially in the fields of electronic &
plumbing
USES
1. Used in electrical industry
2. Alloy with 50% tin is general-purpose solder
3. For sealing automotive radiator cores.
4. As fuses for fire-extinguishing equipments,boiler plugs,etc.
Heat treatment of alloys (steel)
Heat treatment is defined as” the process of heating and cooling of solid steel article under
carefully controlled condition”. During heat treatment certain physical properties are altered
without altering its chemical composition
Objectives (or) purpose of heat treatment
Heat treatment causes
i. Improvement in magnetic and electrical properties
ii. Refinement of grain structure
iii. Removal of the imprisoned trapped gases
iv. Removal of internal stress
v. Improves fatique and corrosion resistance

Types of heat treatment of alloys (steel) 1. Annealing

 Annealing means softening. This is done by heating the metal to high temperature
followed by slow cooling in a furnace.
Purpose of annealing
i. It increases the machinability
ii. It also removes the imprisoned gases
Types of annealing
Annealing can be done in two types
i. Low temperature annealing (or) process annealing
ii. High temperature annealing 9or) full annealing
Low temperature annealing (or)process annealing

It involves in heating steel to a temperature below the lower critical point followed
by slow cooling
Purpose
1. It improves mashinability by reliving the internal stress or internal strain
2. It increases ductility and shock resistance
3. It reduce hardness
(i) High temperature annealing (or) fault annealing
It involves in heating to a temperature about 30 to 50⁰C above the higher critical
temperature and holding it at that temperature for sufficient time to allow the
internal changes to take place and then cooled room
temperature
The approximate annealing temperature of various grades of carbon steel
are
1. Mild steel=840-870⁰c
2. Medium carbon steel=780-840⁰c
3. High carbon steel=760-780⁰c
Purpose

1. It increases the ductility and machinability

2. It makes the steel softer, together with an appreciable increases in its toughness

2.Hardening (or) quenching

 It is the process of heating steel beyond the critical temperature and then suddenly
cooling it either in oil or brine water or some other fluid. 
 The faster the rate of cooling harder will be the steel produced. 
 Medium and high carbon steel can be hardened but low carbon steel cannot
hardened 
Purpose
1. It increases its resistance to wear ability ,to cut other metal and strength .
2. It increases abrasion resistance.
3. Used for making cutting tools.
3. TEMPERING
 It is the process of heating the already hardened steel to a temperature lower than
its own hardening temperature & then cooling it slowly. 
 The reheating controls the development of the final properties 
 Thus, 
(a)For retaining strength & hardness, reheating temperature should not exceed
400⁰C.
(b) For developing better ductility & toughness, reheating temperature should be
within 400-600⁰C.
Purpose
1. It removes stress &strains that might have developed during quenching.
2. Increased toughness & ductility.
 3. Used for cutting tools like blade,cutters etc.
4. NORMALISING
It is the purpose of heating steel to a definite temperature (above its higher
critical temperature) & allowing it to cool gradually in air. Purpose
1. Recovers homogeneity
2. Refines grains.
3. Removes internal stresses
4. Increases toughness
5. Used in engineering works
NOTE: The difference between normalised & annealed steel are
1. A normaled steel will not be as soft as annealed steel.
2. Also normalizing takes much lesser time than annealing.
5.CARBURIZING
 The mild steel article is taken in a cast iron box within containing small pieces of
charcoal(carbon material). 
 It is heated to about 900 to 950⁰C & allow it for sufficient time,so that the carbon is
absorbed to required depth . 
 The article is then allowed to cool slowly within the box itself. 
 The outer skin of the article is converted into high carbon steel containing 
about 0.8 to 1.2% carbon. Purpose
To produce hard surface on steel article

6.NITRIDING
 Nitriding is the process of heating the metal alloy in presence of ammonia
to about 550⁰C. 
 The nitrogen (obtained by the dissociation of ammonia) combines with the
surface of the alloy to form hard nitride. 
Purpose
To get super-hard surface.

UNIT V
NANO CHEMISTRY
PART-A
1. What are nano particles?
Nanoparticles are particles having size of which ranges from 1-50 nm.
2.What are nano materials?
Nanomaterials are the materials having components with size less than 100 nm at least in one dimension.
3. Define nano-wires.
Nano-wire is a material having an aspect ratio ie., length to width ratio greater than 20. They are also referred to as
quantum wires.
4. What is nano –rod?
Nano- rod is a material having an aspect ratio in the range 1 to 20 with short dimension of the material being 10-
100nm.
5. What are nano clusters?
Nano clusters constitute an intermediate state of matter between molecules and bulk materials .
6. What are CNTs?
Carbon nanotubes (CNT) are allotropes of carbon with a nanostructure having a length -to-diameter ratio greater
than 1,000,000.
7. Define nanochemistry.
Nanochemistry is defined as the study of manipulation of materials at atomic molecular and macromolecular
scales.
8.Name the various methods of synthesis of nano-material.
Laser ablation
Chemical vapour depostion
Precipitation
Electro- depostion
 Thermolysis
9.What is CVD?
CVD is Chemical Vapour deposition. It is a process of chemically reacting volatile compound of a material with
other gases, to produce a non-volatile solid that deposits automatically on a suitably placed substrate.
10.Mention the application of Nano-wires.
Nano-wires are used for enhancing mechanical properties of composites.
It is used to prepare active electronic components such as p-n junction and logic gates.
11.What are the characteristics of Nano-rods?
 Nano-rods are two-dimensional materials.
 It also exhibits optical and electrical properties.

12. What is magic number?

It is the number of atoms in the clusters of critical sizes with higher stability.
13.Mention some uses of CNTs.
It is used in battery technology and in industries as catalyst.
It is used in composites, ICs.
CNTs are used effectively inside the human body for drug delivery.

PART-B

1.Explain the properties of Nano-materials.

(i) Melting points:
They have lower melting points and reduced lattice constants.
(ii) Optical properties:
The change in optical properties is caused by two factors.
(a)The quantum confinement of electrons within the nano-particles increases the energy level spacing.
(b)Surface plasma resonance, which is smaller in size for nano-particles than the wavelength of incident radiation.
(iii) Magnetic properties:
Bulk materials have ferro-magnetic properties. When the particle size is reduced ,they get super –
paramagnetic properties.
(iv)Mechanical properties:
Mechanical properties of polymeric materials can be increased by the addition of nano-
fillers.
Nano-materials are stronger, harder and more wear resistant and corrosion resistant.
(v)Electrical properties:
(a)Electrical conductivity decreased in reduced dimension.
(b)Electrical conductivity increased in micro-structure.
(vi) Chemical properties:
In heat treatment of nano material, diffusion of impurities, structural defects, and dislocation increased.
Increased perfection will have increased chemical properties.

2. Discuss the laser ablation ,CVD and electrodeposition techniques for the synthesis ofnano-particles.
Top Down / Physical / Hard Methods:1. Laser Ablation:
Laser Ablation chamber :
High-power laser pulse is used to evaporate the matter from the target .The total mass ablated from the target per
laser pulse is referred to as the ablation rate.
Reaction setup:
When a beam of laser is allowed to irradiate the target, a supersonic jet of particle is evaporated from the target
surface. Simultaneously, an inert gas like Argon, Helium is allowed into the reactor to sweep the evaporated particles
from the furnace zone to the colder collector.
The ablated species condense on the substrate placed opposite to the target. The ablation process takes place in a
vacuum chamber, or in the presence of some background ga
2.Chemical Vapour Deposition (CVD):
In this process volatile compound of a material chemically react with other gases, to produce a non-volatile solid
that deposit on a substrate.
CVD reaction requires activation energy to proceed .This energy can be provided by several methods.
a) Thermal CVD:
The reaction is activated by high temperature above 900o C . b) Plasma CVD:
The reaction is activated by plasma at temperature between 300-700oC.
(c) Laser CVD:
Pyrolysis occurs when laser thermal energy falls on an absorbing substrate.
(d) Photo-laser CVD:
The chemical reaction is induced by UV radiation, which has sufficient photon energy, to break the chemical bond
in the reactant molecules.
Various steps involved in synthesis of CVD are:
1.Transport of gaseous reactant to the surface.
2.Adsorption of gaseous reactant on the surface.
3.Catalysed reaction occurs on the surface.
4.Product diffuses to the growth site.
5.Nucleation and growth occurs on the growth site.
6.Desorption of reaction products away from the surface.
CVD Reactor:
The CVD reactors are of two types
*Hot-wall CVD
*Cold-wall CVD
Hot wall CVD reactors are usually tubular in form and heating is accomplished by surrounding the reactor with
resistance elements.
In cold- wall CVD reactors, substrates are directly heated inductively by graphite subsectors, while chamber walls
are air or water cooled.

3.ELECTRODEPOSITION:
Template assisted electro deposition is an important technique for synthesizing metallic nanomaterials with
controlled shape and size. Arrays of nano-structured materials with, specific arrangements can be prepared by this
method, using an active template cathode in an electrochemical cell. The electrodeposition method consists of an
electrochemical cell. The cell usually contains a reference electrode, a specially designed cathodes and an anode. The
cathode substrate on which elelctrodeposition of the nanostructures, can be made of either non metallic or metallic
materials. By using the surface of the cathode as a template, various desired nanostructures can be synthesized for specific
applications.

3.Describe the synthesis of nanomaterials by precipitation and thermolysis method.

Bottom - up methods /Chemical /soft methods:
It involves building up of nano materials from the bottom by atom by atom (=0.1 nm) or molecule by molecule or
cluster by cluster. This method is carried out by the following process:
1.Precipitation
2.Thermolysis
a)Solvothermal synthesis
b)Hydrothermal synthesis
1. Precipitation method :
Generally nano particles are synthesized by the precipitation reaction between the reactants in presence of water
soluble inorganic stabilizing agent.
Precipitation of BaSO4 Nano particles:
10 g of Sodium hexa meta phosphate (stabilizing agent) was dissolved in 80 ml of distilled water in 250ml beaker
with constant stirring. Then 10ml of 1M sodium sulphate solution was added followed by 10ml of 1M Barium Nitrate (
Ba (NO3)2 )solution .The resulting solution was stirred for 1 hour. The resulting precipitate was then centrifuged, washed
with distilled water and vacuum dried.
Ba(NO3)2 + Na2SO4 BaSO4 ↓+ 2NaNO3 In the absence of stabilizing agent, Bulk BaSO4 is obtained.
Precipitation by reduction :
Reduction of metal salt to the corresponding metal atoms .These atoms act as nucleation centres leading to
formation of atomic clusters. These clusters are surrounded by stabilizing molecule that prevents the atoms
agglomerating.
2. Thermolysis method:
 Thermolysis is characterized by subjecting the metal precursors (usually organometallic compounds in oxidation
state zero) at high temperatures together with a stabilising agent. Nano particles show an increase in size relating to the
temperature size.
This is due to the elimination of stabilizing molecule, generating a greater aggregation of the particles.
Hydrothermal synthesis
a.Hydrothermal synthesis:
It involves crystallization of substances from high temperature aqueous solutions at high vapour pressure.
Hydrothermal synthesis is usually performed below the super critical temperature of water.(3740).
Method:
Hydrothermal synthesis is performed in an apparatus consisting of a steel pressure vessel called autoclave in which a
nutrient is supplied along with water. A gradient of temperature is maintained at the opposite ends of the growth chamber,
so that the hotter end dissolves the nutrient and the cooler end cause seeds to take additional growth.
b. Solvothermal synthesis :
Solvothermal synthesis involves the use of solvent under high temperature (between 100o– 1000oc) and moderate to
high pressure (1 atm to 10,000 atm ) that facilitate the interaction of precursors during synthesis.
Method:
A solvent is mixed with certain metal precursors and the solution mixture is placed in an autoclave kept at
relatively high temperature and pressure in an oven to carry out the crystal growth. The pressure generated in the vessel,
due to the solvent vapour , elevates the boiling point of the solvent.
Eg: Methanol, Ethanol, Toluene, Cyclohexane ,etc.
Solvothermal synthesis of Zinc oxide:
Zinc acetate dehydrate is dissolved in 2-propanol at 50oC. Subsequently the solution is cooled to 0oC and NaOH is
added to form ZnO. The solution is then heated to 65oC to allow ZnO growth for some period of time before a capping
agent (1-dodecanethiol) is injected to the suspension to arrest growth. The rod shaped ZnO nano-crystal is obtained.
Uses:
→Much geometry including thin film, bulk powder, and single crystals can be prepared.
→Thermodynamically stable novel materials can also be prepared easily.

4.Write a short note on Nano wires, Nano rods and Nano clusters.
Nano –wires:
Nano-wire is a material having an aspect ratio i.e. length to width ratio greater than 20. Nano –wires are also
referred to as “quantum wires”.
Nano –Wires of metals: Au ,N i,Pt
Nano –Wires of semiconductors: Si, GaN
Nano –Wires of Insulators: SiO2, TiO2
Molecular Nano –Wires: DNA
Characteristics of Nano- Wires :
>Nano- Wires are one – dimensional material.
>Conductivity of a nano-wire is less than that of the corresponding bulk materials.
>It exhibits distinct optical, chemical, thermal and electrical properties due to this large surface area.
>Silicon nano-wires show strong photoluminescence characteristics.
Synthesis of nanowires:
1. Template assisted synthesis:
The templates contain very small cylindrical pores or voids within the host material and the empty spaces are filled
with the chosen material to form nanowires.
Eg. Mesoporous Alumina
2.VLS method:
This method is used for the production of single crystal of semiconductors of elemental Silicon and Germanium.
The mechanism involves a gas phase reaction followed by anisotropic crystal growth (different properties in different
directions). For example the laser ablation and thermal evaporation of a solid target made of pure Si powder mixed with
metals (Fe, Co, Ni) catalyst at 1200o -1400o C followed by condensation on a substrate maintained at 900o-1100o C
facilitates the growth of long Si nanowires with diameters in the range of 20-80 nm. Each wire consists of crystalline Si
core encased by an outer layer of silicon dioxide.
Applications of nanowires:
Nanowires are used to enhance mechanical properties of composites.
Semiconductor nanowires are used as components in making transistors, diodes, logic gates and digital computing.
Nanowires find applications in high density data storage either as magnetic read heads.
Nano Rods:
Nano rods are a material having an aspect ratio in the range 1 to 20 nm.
Characteristics of Nano rods:
 It exhibits special optical and electrical properties. Nano rods are two dimensional materials.
Synthesis of Nano rods: Direct chemical synthesis:
Metal atoms are combined with ligands which act as shape control agents which make bonds with different metal
atoms of different strength to get nano rods.
Applications of nanorods:
Nano rods are used in display technology and micromechanical switches.
Nano clusters:
Nano clusters are multi atom particles of size intermediate between molecule and bulk materials. The size of nano
clusters range from 1-10nm .The atoms or molecules in a clusters are bound by any of the forces like covalent, ionic,
Vander waal’s forces. When a gas condenses in to cluster of atoms the no. of atoms in these clusters varies between a few
to hundreds. Clusters of certain size called critical size are more stable than others (200-103 atoms).
The no. of atoms in a cluster of critical size with higher stability is called Magic number. Cluster of transition
metal atoms have chemical, electronic, magnetic properties which vary with number of constituent atoms.
Source of clusters:
Super sonic nozzle source:
The metal is vaporized in an oven and mixed with inert carrier gas at a pressure of several atmospheres at a
temperature of 75-1500K .Metal/ Carrier gas mixture is allowed to pass through the nozzle in to high vacuum which
produces a supersonic beam of the mixture. The carrier gas produces large clusters. In the absence of carrier gas small
clusters are produced.
Gas aggregation source:
Vapours of metal atoms are introduced in to inert gas which is maintained at high pressure and high temperature.
The gas phase is supersaturated with metallic species and aggregates. It acts as a seed and produces a continuous beam of
nano clusters.

5. Discuss the application of Nano materials in various fields.Applications of Nano materials:

Industries
1. As catalyst:
The nano materials have more no. of surface atoms which make them catalytically active. For example, bulk gold
chemically inert white nano gold possess excellent catalytic property.
2. Water purification:
Dissolved salts and colour producing organic compounds can be filtered very easily from water by using nano porous
membrane having pores smaller than 10nm.Magnetic nano particles are used to remove heavy metal contamination from
waste water.
3. In Fabric industry:
Embedding of Nano particles on fabrics make them stain repellent. Socks embedded with silver nano particles
remove the bacteria and makes them odour free.
4. In automobiles:
Fuel consumption in automobiles can be reduced by using specially designed nano particles as fuel additives.
Incorporation of small amount of nano particles in car bumpers make them stronger than steel
5. In food industry:
Nano particles are used to make packing material and containers to store food.
6. In Solar cells:
Absorption of solar radiation in solar cells containing nano particles are higher than the bulk materials.
Medicine :
1. Nano drugs:
Nano materials are used as drugs for the treatment of cancer and TB.
2. Nano medibots :
Nano particles act as nano medibots which identify and penetrate the cancer cells and destroy them by supplying anti
cancer drugs
3.Gold coated Nano shells:
Gold coated nano shells containing silicon core are administered near the tumours .
When IR light is irradiated on the skin externally, the gold nano shells absorb the light and convert in to heat which
destroys the cancer cells responsible for tumour.
4. Gold nano particles as sensors:
 Nano gold when mixed with different type microorganisms show different colours which is used to identify the
harmless and dangerous micro organisms.
5.Protein analysis:
Gold nano particles injected in to the body reacts with the protein and the protein
concentration can be detected by passing laser beam externally.
6. Gold nano shells for blood Immune assay:
Gold nano shells are used to detect WBC count in blood.
7. Gold nano shells in Imaging:
Gold nano shells is used as a scanning probe which gives the magnified image of cells in a body
8. Targetted drug delivery:
It involves slow and selective release of drug to the targeted organs.
Electronics:
1.Quantum wires have electrical conductivity
2.Nano radios are produced by using CNT
3.MOSFET (Metal Oxide Semiconductor Field Effect Transistor) is used for Amplifying and switching electronic signals.
4.Nano wires are used to build transistors without p-n junction diode.
5.Transistor called NOMFET (Nano particle Organic Memory Field effect transistor) is created by combining Gold nano
particles with organic molecules
Biomaterials:
1.Nano materials are used as bone cement and bone plates in hospitals
2.It is used as material for joint replacement
3.It is used in the manufacture of some components like heart valves, contact lenses, dental implants etc.
6.Write a short note on CNT.
Carbon NanoTubes ( CNTs) :
CNTs are allotropes of carbon in the form of molecular scale tubes made of graphitic carbon with unique
mechanical and electrical / electronic properties with potential applications in electronic, information technology and
medical fields.
Carbon nanotubes were discovered by Sumio Iijima 1991, while preparing C60molecules by the carbon arc
process. They are also known as tubular fullerenes and are cylindrical graphene sheets of sp2 bonded carbon atoms.
These nanotubes are single molecules measuring few nanometers in diameter and several microns in length. Depending
on the growth process, the length of the tubes can be 100 nanometers to several microns (1 micron = 1000 nm), the
diameter varying from 1 to 20 nanometers
Structure of CNTs:
Carbon nanotube is a tabular form of carbon with 1-3 nm diameters and a length of few nm to microns. Each carbon
atom in the carbon nanotubes is linked by the covalent bond. They are two types of nanotubes.
1. Single walled carbon nanotubes (SWCNT) having a diameter of 1 nm. Three types of SWCNTs are as follows:
2. Multi-walled nanotubes (MWNTs) or nested nanotubes consist of multiple layers of graphite rolled to form tube
shape.
MutliwalledNanotube
Synthesis of Carbon Nano Tubes:
Carbon nanotubes are prepared by the following methods.
Pyrolysis of hydrocarbons.
Laser evaporation
Carbon arc method.
Chemical vapour decomposition.
Pyrolysis of Hydrocarbon:
Carbon nano tubes are synthesized by the pyrolysis of hydrocarbons such as acetylene at about 700oC in the
presence of Fe-Silica or Fe-graphite catalyst under inert conditions.
Laser Evaporation:
It involves vapourization of graphite target, containing small amount of cobalt and nickel, by exposing it to
an intense pulsed laser beam at higher temperature (1200oC) in a quartz tube reactor. An inert gas such as argon is
simultaneously allowed to pass into the reactor to sweep the evaporated carbon atoms from the furnace to the colder
collector, on which they condense as carbon nanotubes.
Carbon arc Method:
It is carried out by applying direct current (60-100 A and 20 – 25 V) arc between graphite electrodes of 10-20 µm
diameters. The discharge vapourizes one of the carbon rods and forms a small rod- shaped deposit on the other rod. The
yield depends on the uniformity
 of the plasma arc and the temperature. The deposits contain 10 – 50 SWNTs, the average size about 1.4 nm in diameter
and about 10 µm in length.
Chemical Vapour Deposition:
It involves decomposition of vapour of hydrocarbons such as methane, acetylene, ethylene, etc., at high
temperatures (1100oC) in presence of metal nanoparticle catalyst like nickel, cobalt, iron supported on MgO or Al2O3.
Carbon atoms produced by the decomposition condense on a cooler surface of the catalyst.
Properties of CNTs:
(1) Mechanical Properties:
Young’s modulus of carbon nano tubes is 10 times greater than that of steel. CNTs have very structural defects in
their walls, and hence, do not fracture on bending. The tensile strength of CNTs is about about 20 times that of steel.
(2)Electrical Properties:
The electrical properties of CNTs vary between metallic to semiconducting materials.
The very high electrical conductivity of CNT is due to the minimum defects in the structure.
(3)Thermal Conductivity:
The thermal conductivity of CNT is very high due to the vibration of covalent bonds
due to minimum defects in the structure.
Applications of Carbon NanoTubes:
Due to the unusual and unique properties of CNTs they find potential applications in the following field:
Carbon nanotubes play an important role in the battery technology, because some charge carriers can be successfully
stored inside the nanotubes.
Multi-walled CNTs can be used as storage devices to store hydrogen gas in fuel cells.
CNTs are used as catalyst in chemical reactions.
CNTs can be used for drug delivery within the body by placing the drugs within the tubes or by attaching the drug to the
sides of the tubes.
CNTs are used as light weight shielding materials to protect electronic equipments from electromagnetic radiation.