I B.E.

, ENGINEERING CHEMISTRY

Unit-I -WATER TECHNOLOGY AND CORROSION

PART-A (2 marks)
1. Define hardness of water.
Hardness is the characteristic property present in water. This prevents lather formation
with soap solution.
2. Distinguish between carbonate hardness and noncarbonate hardness.
S.No. carbonate hardness noncarbonate hardness
1 It is temporary hardness It is permanent hardness
2 It can be removed on boiling It can’t be removed on boiling
3 Due to the presence of carbonates Due to the presence of chlorides
and bicarbonates of calcium and and sulphates of calcium and
magnesium magnesium.

3. Draw the structure of EDTA. What happens when EDTA is added to hard water?

(Ca2+or Mg2+) + EBT (Ca2+ + Mg2+) EBT

Wine red colour
(Ca2+ + Mg2+)EBT + EDTA (Ca2+ + Mg2+) EDTA + EBT
Steel blue colour
4. Mention the common units used for expressing hardness of water.
1. Parts per million (ppm)
2. Milligrams per liter (mg/l)
3. Degree clerk (0Cl)
4. Degree French (0Fr)
5. Why hardness is expressed interms of CaCO3 equivalents? Give reason
 Molecular weight of CaCO3 = 100
 Stable under high temperature
 The most insoluble one.
6. Name any two Coagulants.
Aluminum sulfate (Alum) Al2(SO4)3 · 14 H2O
Sodium aluminate Na2Al2O4
Ferrous sulfate FeSO4 · 7 H2O
Ferric chloride FeCl3 · 6 H2O
7. What is meant by priming and foaming? How can they be prevented?
Priming is the process of production of wet steam and the formation of stable bubbles
above the surface of water is called foaming.
8. The presence of CO2 in boiler feed water should be avoided. Why?
Dissolved carbon dioxide in water produces carbonic acid, which is acidic and corrosive
in nature.
CO2 + H2O H2CO3
9. Indicate the reasons for boiler corrosion.
Due to the presence of dissolved Oxygen, dissolved carbon dioxide and dissolved MgCl2
boiler corrosion takes place.
10. What is electrodialysis?
Electro dialysis is the process of separating ions of the salt from the salt water through
ion-selective membranes by passing direct current.
11. How is exhausted ion-exchange resins regenerated?
When the cation exchange resin is exhausted, it can be regenerated by passing a solution
of dil.HCl or dil.H2SO4.
RCa + 2HCl RH2 + CaCl2
Similarly, when the anion exchange resin is exhausted, it can be regenerated by passing a
solution of dil.NaOH.
R’Cl2 + 2NaOH R’(OH)2 + 2NaCl
12. Define desalination
Removal of common salt from sea water is known as desalination process
13. Write the principle involved in the desalination of water by reverse osmosis.
If a hydrostatic pressure in excess of osmotic pressure is applied on the higher concentration
side, the solvent flow is reversed. i.e., solvent flows from higher concentration to lower
concentration. This principle involved in the desalination of water by reverse osmosis.
14. Mention requisites of potable water.
Type Amount
Hardness < 0.2 ppm
Soda alkalinity 0.15 – 1.0 ppm
Caustic alkalinity 0.15 – 0.45 ppm
Excess soda ash 0.3 – 0.55 ppm
Dissolved gases like O2, CO2 0 ppm

15. What is residual chlorine?

Residual chlorine is the amount of chlorine that remains (unreacted) in the water after certain
period.
16. Define the term break-point chlorination.
The point at which the pathogenic bacterias are killed by the released free chlorine and
the residual chlorine appears is known as break-point chlorination.
17. What are the factors which affect corrosion?
1. Nature of the metal - (i) Position in the galvanic series, (ii) Relative areas of the anode and
cathode (iii) Over potential (iv) Purity of metals (v) Physical state of metals (vi) Nature of
the surface film
2. Nature of the environment - (i) Temperature, (ii) Humidity, (iii) corrosive gases, (iv) pH,
18. Bolt and nut made of the same metal is preferred in practice. Why?
When two different metals are in contact with each other in presence of an aqueous solution
or moisture, galvanic corrosion occurs.
19. What is cathodic protection?
It is protection of parent metals from corrosion by connecting it with a more active metal
like Mg, Al etc. The connected active metal undergoes corrosion, thereby protecting the parent
metal from corrosion.
20. What is electrochemical corrosion?
When a metal is in contact with one or two dissimilar metals or alloys or solution
partially or fully corrosion takes place. This type of corrosion is known as electrochemical
corrosion.

Unit I
PART-B (16 Marks)
1. (i) What is the principle of EDTA method? Describe the estimation of hardness of water
by EDTA method. (12)
a) Principle --- 3 marks
b) Structure ---- 1 mark
c) 3 titrations ---- 4 marks
d) Calculations ---4 marks
(ii) What are the various methods by which disinfection of domestic water is carried out?
Explain. (4)
a) Name of the disinfectants --- 2 marks
b) Methods -------2 marks
2. (i) Describe briefly the different steps in the purification of water for drinking
purposes. (10)
For each step ---2 marks
(ii) What is desalination? Name the different methods of desalination. Explain any one in
detail. (6)
a) Definition --- 2 marks
b) Methods -------4 marks
3.(i) Discuss briefly about the problems caused due to the usage of hard water in boilers.
(8)
a) Definition for boiler feed water --- 2 marks
b) Problems discussion -----6 marks
(ii) What are Zeolites? How do they function in removing the hardness? (8)
a) What is Zeolites --- 2 marks
b) diagram ---- 2 marks
c) function ---- 4 marks

4. (i) How is internal treatment of boiler water carried out? (8)

a) What is internal treatment --- 2 marks
b) any 3 methods -------- 6 marks
(ii) Describe the principle and method involved in the determination of different types and
amount of alkalinity of water (8)
a) Principle -----2 marks
b) Phenolphthalein alkalinity ----- 2 marks
c) Methyl Orange alkalinity ----- 2 marks
d) Calculation ------ 2 marks
5. (i)Explain the desalination of water by reverse osmosis method (8)
a) Diagram ---- 2 marks

b) RO definition --- 2 marks

c) Hydrostatic pressure ---- 1 marks
d) Process ---- 3 marks
(ii)Describe demineralization process of water softening. Explain the reactions
involved. (8)
a) Diagram ---- 1 mark
b) What is demineralization process ---- 2 marks
c) Process ----- 3 marks
d) Regeneration ----- 2 marks

6. (i)What is meant by sterilization of water? Explain how sterilization of water is carried

out by using chlorine and ozone. (8)
a) Sterilization of water ---- 4 marks
b) For each method ------ 2 marks
(ii) Define alkalinity. How is it determined? (8)
a) Definition ----- 2 marks
b) Determination ---- 6 marks
7. i) What is potable water? What are the steps taken to obtain drinking water?
(8)
a) What is potable water ----- 2 marks
b) For each step ------ 1 mark
ii) Explain scale and sludge formation. (8)
a) Scale definition ----- 1mark
b) Disadvantages ------ 3 marks
c) Sludge definition ----- 1mark
b) Disadvantages ------ 3 marks
8. Define corrosion of metals. What are different types of corrosion? Explain theory of wet
corrosion, giving its mechanism. (16)
a) Definition ---- 1mark
b) Naming the types and explanation ----5marks
c) Oxygen absorption theory ----- 5marks
d) Hydrogen Evolution theory -----5marks
9. i) Differentiate between chemical corrosion and electrochemical corrosion. (8)
Meaning of types, examples, types and reactions
ii) Illustrate the reactions involved in differential aeration corrosion with reference to the
iron materials. (8)
Reactions with examples
10. i) Write in brief on impressed current method of cathodic protection. (8)
ii) Explain sacrificial anode method. (8)
a) Diagram ---- 2 marks
b) Explanation ---- 6 marks

Unit II-Electrochemistry, Batteries and fuel cells

Part -A
1. Define electrode potential.
At equilibrium, the potential difference between the metal and solution becomes a
constant value and is termed as “electrode potential.”
2. Distinguish electrolytic and electrochemical cell.
S. No Electrolytic cells Electrochemical cells
1. In electrolytic cells current is In electrochemical cells, current is
passed through an electrolyte produced from electrolyte solutions.
solution.
2. In electrolytic cells the cathode is In electrochemical cells during discharge
negative (-) and anode is positive of current, the cathode is positive (+) and
(+). anode is negative (-).
3. In electrolytic cells the cathode is In electrochemical cells the half cell with
negative (- ve) and attracts the electrode having reduction reaction is
cations or positive (+ ve) ions. always cathode and positive (+ ve). The
And attracts the anions or negative half cell with electrode having oxidation
(- ve) ions. reaction is always anode which is negative
(- ve). This is applicable for the discharge
reaction or discharging of current.

4. Examples of electrolytic cells are Good examples of electrochemical cells

mainly are mainly
(a) i. Electroplating (a) i. Voltaic cells or Batteries
(b) ii. Extraction or purification of (b) ii. Corrosion process.
metals.

3. What is Helmholtz’s double layer?

When a metal is placed in the solution of its own salt, oxidation or reduction takes place
and ultimately a dynamic equilibrium is established, because negative or positive charge
developed on the metal attracts the positively or negatively charged free ions in the solution. Due
to this attraction, the positive or negative ions remain quite close to the metal. Thus, a sort of
layer (positive or negative ions) is formed, all around the metal. This layer is called “Helmholtz
electrical double layer.”
4. State Ostwald’s dilution law.
The variation of the degree of dissociation with dilution is known as Ostwald’s dilution law.
5. Define Oxidation and Reduction.
When a metal lose its electrons is called an Oxidation where as when a metal gain
electrons is called Reduction.
6. What is relaxation effect?
 7. Write Nernst equation and explain the terms involved.
E = E0 +0.0591/n log [Mn+]
Where n = no of electrons
F = Faraday
E = Electrode potential
E0 = Standard Electrode potential
R = gas constant =8.134 J/K/mole

8. Calculate the standard emf for the cell Zn/ZnSO4//CuSO4/Cu. Standard reduction
potential for Zn2+/Zn and Cu2+/Cu are -0.763V and +0.337V respectively.
E0cell = ER – EL = E0 Cu2+/ Cu - E0 Zn2+/ Zn]
= 0.34V-(-0.76V)
= 1.1 V
9. Why is the salt bridge used in the construction of a cell?
Salt bridge serves as a bridge to complete the electric circuit, maintain electro neutrality
of electrolyte and minimize the liquid junction potential. For precise measurements of
potential, a salt bridge is used.
10. What are the conditions for an electrochemical cell to act as a standard cell?
A standard cell is one which is capable of giving constant and reproducible e.m.f. and has
a negligible temperature coefficient of the e.m.f.
11. What is galvanic series?
Electrode potentials of various metals and their alloys in common use are measured by
immersing them partially in the sea water and the values have been arranged in the
decreasing order of activity and it is called galvanic series.
12. What is the significance of electrochemical series? Mention any two uses.
1. Relative ease of oxidation or reduction: The metals on the top are more active, easily
ionized into solution and they are good electron donors.
2. Corrosion: The metal higher in the series is anodic or more active and they are more prone
to corrosion. The metals lower in the series are noble metals and they are less prone to corrosion.
3. Liberation of Hydrogen: The metal with –ve potential will displace H2 from an acid
solution i.e., active metals are attacked by acids
 4. Replacement tendency: The metals which are more active will displace less active ion
from the solution of its salt

13. What is standard electrode potential?

It is the measure of tendency of a metallic electrode to lose or gain electrons, when it is in
contact with a solution of its own salt of unit molar concentration at 250C.

14. Define a reference electrode with an example.

The electrode of standard potential, with which we can compare the potentials of other
electrodes is called reference electrode.
Ex :standard hydrogen electrode, whose electrode potential at all temperatures is taken as
zero.

15. What is calomel electrode?

Calomel electrode is the mercury-mercurous chloride electrode. The potential of the calomel
electrode, on the hydrogen scale has been found to vary with the concentration of the
potassium chloride solution used. When the KCl solution is 0.1N, 1.0N and saturated, it is
called respectively as decinormal, normal and saturated calomel electrode.

16. What are the advantages of storage batteries?

As the redox reactions are reversible in storage batteries, they can be recharged again and
again.

17. State the reaction when a lead storage battery is recharged?

The reaction when a lead storage battery is recharged,

Pb(s) + SO42-(aq) PbSO4(s) + 2e-

PbO2(s) + 4H(aq) + SO42-(aq) 2e- PbSO4(s) + 2H2O(l)

18. What are secondary cells? Give an example.

 A rechargeable battery, storage battery, or accumulator is a type of electrical battery. It
comprises one or more electrochemical cells, and is a type of energy accumulator.
Electrochemical reactions are electrically reversible in these cells.
19. What is a fuel cell? What are its advantages?
A fuel cell is a device that generates electricity by a chemical reaction. Hydrogen is the
basic fuel and fuel cells also require oxygen. They generate electricity with very little pollution
and the by-product produced is water
20. Write the chemical reactions taking place at cathode and anode in hydrogen oxygen
fuel cell.
The chemical reactions taking place at cathode and anode in hydrogen oxygen fuel cell is,
Anode: 2H2+4OH-(aq) 4 H2O +4e-
Cathode: O2(g)+2H2O(l) 4OH-

PART-B (16 Marks)

1. (a) Derive Ostwald’s dilution law (8)
a)Derivation with explanation ----- 8 marks.
(b) Discuss Debye-Huckle’s theory (8)
a) Failure of Ostwald’s dilution law ----- 2 marks
b) theory with relaxation effect and electrophoretic effect -----6 marks
2. What is electrochemical cell? Explain the Chemical reactions involved. (16)
a) Diagram ----- 2 marks
b) Explanation with reactions-----14 marks
3. Discuss in brief about any two types of electrodes. (16)
a) For each diagram -----2 marks
b) Explanation of each ----7 marks
4. Explain the determination of EMF by Poggendorff’s method. (16)
a) Diagram ----- 2 marks
b) Explanation ---- 14 marks
5. Derive Nernst equation for a cell? Discuss in detail any two applications. Explain the
various terms involved. (16)
a) Derivation---- 10 marks
 b) For each application --- 2 marks
c) Explanation of Terms -----2 marks
6. (a). What is standard electrode potential? Give its importance. (8)
a) Standard electrode potential ---- 2 marks
b) Importance -------6marks
(b). Calculate the EMF of the cell Mg/Mg2+ //Cd2+ (aq) /Cd(s) at 250C when
[ Cd2+]=0.7M, [Mg2+] =1.0M and E0cell =1.97 V (8)

7. Discuss the electrochemical series and its applications. (16)

a) Electrochemical series meaning ----- 2 marks
b) Discussion of reduction and oxidation potential and their arrangement ---10 marks
c) Advantages ----- 4 marks
8. With an example explain any one of the primary cell. (16)
a) Meaning of primary cell ------2 marks
b) Explanation with reaction and example ----- 14 marks
9. Write short notes on Secondary battery and its charging and discharging. (16)
a) Meaning of secondary cell ---- 2 marks
b) Example and discussion ----- 8 marks
c) Charging and discharging ----- 4 marks
d) advantages over primary cell ---- 2 marks
10. Describe the construction and working of Hydrogen-oxygen fuel cell. (16)
a)What is Fuel Cell --- 2 marks
b) Construction ---- 6 marks
c) Diagram ----2 marks
d) Working ----6 marks

Unit- III - CHEMISTRY OF ADVANCED MATERIALS

PART-A (2 Marks)
1. Write a note on any one special cement.
Water proof cement
Water proof cement is obtained by adding water proofing substances (calcium stearate,
aluminium stearate and gypsum with tannic acid) to ordinary Portland cement, during grinding.
 Functions: to make concrete impervious to water under pressure and to resist the
absorption of water
2. What are the raw materials for manufacture of cement?
i. Calcaerous materials CaO (limestone, chalk, marl)
ii. Argillaceous materials Al2O3 and SiO2 (clay, shale, slate)
iii. Powdered coal or fuel oil
iv. Gypsum(CaSO4.2H2O)
3. What is plaster of paris? Write it uses.
CaSO4. ½ H2O – plaster of paris is produced by heating fairly pure gypsum to a temperature
of about 120 -160 C.
Functions:

i. Enhances the initial setting time of cement and later retards the time.

ii. Used in making casting structural tiles and in surgical bandages.

4. Define refractory. Give example.

Refractories are materials that can withstand high temperatures without softening or
deformation in shape.
5. What is RUL?
Refractory under Load - Ability of a material to withstand high temperature, without
appreciable deformation in shape or softening under particular operating condition
6. Why is dolomite bricks rarely used as refractories?
Dolamite bricks possess low strength, high porosity, greater shrinkage, high hygroscopicity
and softness, so they are rarely used as direct refractories.

7. Mention the role of antioxidants in lubrication process.

Adding antioxidants to oil retards oxidation by getting themselves oxidized. They are
particularly added in lubricants used in internal combustion engines, turbines, etc. where
oxidation of oil is serious problem, the antioxidants are aromatic phenolic or amino compounds.
8. Why are plastics indispensible in every day life?
 Lightness in weight, corrosion resistance, low fabrication cost, good thermal and electrical
insulation process, low thermal expansion coefficient, decorative effect, easily and quick
moulding.
9. Define viscosity index.
It is defined as the average decrease in viscosity of oil per degree rise in temperature
between 100F and 210F. If the increase in temperature makes notable decrease in the viscosity of
the lubricating oil then the oil has a low viscosity index. A good lubricant should have high
viscosity index.
10. Write the significance of cloud point.
Cloud point is useful for estimating the temperature at which filter screens in the fuel
intake system of diesel engine might become clogged because of wax separation.
11. Synthetic lubricants have added advantage over natural lubricant. Why?
1. Natural lubricants undergo oxidation easily and have a tendency to hydrolyze.
2. But synthetic lubricant having high flash point, high viscosity, high thermal stability
and very low freezing point.
12. Write the uses of organic electronic materials

1. Organic electronics can be used as organic semiconductors, organic dielectrics,

conductors and light emitters.

2. It can be used as smart windows and electronic paper.

3. Conductive polymers are expected to play an important role in the emerging science
of molecular computers.

13. Write a note on organic light-emitting diode

An OLED (organic light-emitting diode) is a light-emitting diode (LED) in which the

emissive electroluminescent layer is a film of organic compound which emits light in response to
an electric current.

14. What is degree of polymerization?

The number of repeating units in a chain of polymer is known as degree of
polymerization
15. What is meant by functionality of polymer?
The number of binding sites in a monomer is referred as its functionality.
16. What is thermocol?
Thermocole is a foamed-plastic, obtained by blowing air or gas through molten poly
styrene or poly urethane.
Uses
a) As protecting screens in radars
b) Decorative purposes
c) Used as insulating and vapour barrier
17. Write any four uses of fibres.
 Fibers are important in the biology of both plants and animals, for holding tissues
together.
 The strength and elasticity of spider silk makes it the toughest natural fiber.
 The wind-resistant and wrinkle-free natural fiber is ideal for travel.
 The fiber material is used commonly in the manufacture of fiber optics.
 Resists rain and snow, and since the fiber is hollow, it offers maximum insulation
without bulk. Etc.,

18. What are fullerenes?

A fullerene is any molecule composed entirely of carbon, in the form of hollow sphere,
ellipsoid or tube.
19. Mention a few characteristics of composites.
Higher strength, lower specific gravity, ability to withstand high temperatures, toughness,
thermal shock resistance, easily fabricable, lower electrical conductivity, lower thermal
expansion and better corrosion resistance
20. Define nanomaterials.
The substances in which the particle sizes are in the 1-100nm ranges, they are generally
called nanoparticles or nanomaterials A nanometer is one millionth of a millimeter -
approximately 100,000 times smaller than the diameter of a human hair.
 Unit -III
1. Explain the process of manufacture of Portland cement. (16)
a) Raw materials ----- 2 marks
b) Wet process----- 4 marks
c) Dry process ----- 4marks
d) Flow chart and explanation ----- 6 marks

2. (a). Write a note on setting and hardening of cement. (8)

a) Setting ---- 4 marks
b) hardening ----- 4 marks
(b). Write the functions of raw materials of cement. (8)
a) Naming ----- 2 marks
b) Functioning ----- 6 marks
3. What are refractories? What are the requisites of a material to be used as refractory?
Write a note on acid and basic refractory. (16)
a) Refractory meaning ----- 2 marks
b) Requisites of materials ------ 8 marks
c) For each refractory ----- 3 marks
4. Write descriptive notes on conducting polymer and shape memory alloys. (16)
For each division ---- 8 marks (only meaning, classification, examples and applications)
5. Explain the structure of graphite and molybdenum disulphide. Why this can be used
as solid lubricants. Write their uses. (16)
a) For each diagram ---- 2 marks
b) Explanation ----- 6 marks
c) Reaction ----- 4 marks
d) Uses ----- 4 marks
6. What are composites? Write a note on various applications of composite materials.
(16)
a) Composites ----- 3 marks
b) Examples ------ 2marks
c) Applications ---- 11 marks
 7. Give brief idea of the following i) Solid oxide materials ii)Organic electronic
materials (16)
a) For each division ---- 8 marks (only meaning, classification, examples and applications)
8. (a). Write the uses of the following
i. PVC ii. TEFLON iii. NYLON 6:6 iv. Buna S rubber (8)
a) For each uses ---- 2marks
(b). Distinguish between thermoplastic and thermosetting polymers or resins. (8)
a) minimum 4 differences with examples
9. (a). What are ceramics and how they are classified? Write the uses of ceramics.(8)
a) Meaning of ceramic ---- 2 marks
b) Classification ----- 3 marks
c) uses ------ 3 marks
(b). Write the applications of fullerenes. (8)
Applications ---- 8 marks
10. (a). Discuss in detail the applications of nanomaterials. (8)
Applications ---- 8 marks
(b). Give short notes on fibers. (8)
Meaning, classification, examples and applications

Unit – IV - PHASE EQULIBRIA & NUCLEAR CHEMISTRY

PART – A (2 Marks)
1. State phase rule.
The number of degree of freedom (F) of the system is related to number of components (C)
and number of phases (P) when they are influenced by pressure, temperature and
concentration and they are not influenced by gravity or electrical or magnetic forces at
equilibrium, then phase rule equation can be written as.
F=C–P+2
2. Mention the merits of phase rule.
Phase rule predicts that under given set of conditions
Whether various substances would exist together in equilibrium
 Whether some of the substances would be inter converted Or some of the substances will
completely disappear, this also helpful for studying and controlling various processes such as
Phase separation, Solidification of metals, the change of structure during heat treatment.
3. Define phase with example
A phase is (P) a physically distinct and mechanically separable part of a system which is
separated from other parts of the system by definite boundaries.
Eg. A gas and gas mixture consists of single phase, since there is no demarcation.
CaCO3 solid decomposes to CaO solid and CO2 gas- two solids and gaseous phase –ie it has
3 phases.
4. Define component with example
The Number of components of a system is the smallest number of independently variable
constituents are in equilibrium

5. What is meant by degree of freedom?

It is defined as, “the minimum number of independent variable factors such as temperature,
pressure and concentration, which must be fixed in order to define the system completely”.
Example

Ice(s) Water(l) Water Vapour(g)

If all the three phases are at equilibrium at a point, no degrees of freedom can be altered.
Hence the degree of freedom is zero.
If liquid water is in equilibrium with water vapour, temperature or pressure has to be
fixed to define the system the degree of freedom is one.
For gaseous phase mixture both pressure and temperature have to be fixed in defining
the system. Hence the degrees of freedom will become two.
6. A system consists of benzene and water. What is the number of phases?
As benzene and water are immiscible liquids at room temperature, so the system has .
two liquid phases
7. How many components are present when NH4Cl is heated in a closed vessel?
 Ammonium chloride dissociates into equivalent amount of ammonia gas and hydrogen
chloride gas. The composition can be explained in both the phases by NH4Cl. Hence the
number of component is one.

NH4Cl NH3(g) + HCl(g) ,

8. What is triple point? State its characteristics.
The triple point of a substance is the temperature and pressure at which the three phases (gas,
liquid, and solid) of that substance coexist in thermodynamic equilibrium. For example, the
triple point of water obtained at the temperature 0.00980C and pressure 4.58mm. Any slight
changes in Temperature (or) Pressure will cause any one of the phases to disappear. Hence
the system is invariant.
.
Ice(S) Water(l) Water vapour(V)
Applying phase rule to this point T , F = C-P+2 , =1-3+2=0

9. How many phases and components are existing at triple point in ice – water – water vapour
system.
In Triple point of water exists in there are Three phases ( Solid-Ice, Liquid & Gas – Vapour)
and one component ie H2O
10. State reduced phase rule
For two component system when C=2 and P=1 (min) the F is given by,
F = C-P+2 , F =2-1+2=3
Three variable Temperature, Pressure and Concentration must be specified in order to
describe a two component system. When the pressure of the system constant, then the phase
rule equation becomes F=C-P+1 is called condensed phase rule” or Reduced Phase rule.
11. What is pattinson’s process?
Desilverisation of lead is generally done by pattinson’s process.The argentiferrous lead
contains very small percentage of silver.The argentiferrous lead is heated above its melting
temperature,so that system consists of only liquid phase.
The process of increasing of relative proportion of silver in the alloy is known as pattinson’s
process
12. Calculate the degree of freedom for 2 H2(g) + O2(g) ----2 H2O(v)
It is defined as, “the minimum number of independent variable factors such as temperature,
pressure and concentration, which must be fixed in order to define the system completely”.
F = C-P+2 , Number of Phases 1 ( all are gaseous phase) one component VIZ H2O
F=1-1+2, F = 2

13. Define nuclear fission.

Nuclear fission is the process of splitting of a heavy nucleus into two approximately equal
parts, with simultaneous liberation of a huge amount of energy. Example - fission of U-235
by neutrons.

1
0 n + 23592 U 140
56 Ba + 9336 Kr + 3 10 n + energy.

14. Define nuclear fusion.

Nuclear fusion is a nuclear reaction in which two light nuclei combine to form heavier nuclei
with the simultaneous release of energy. Fusion reactions are the main source of energy for
the sun’

1
1 H + 11 H 2
1 H + 01 e + .

15. List out the health effects of nuclear radiation.

 Radiation from nuclear energy emissions affects humans and other animals in a similar way
as it does plants. It affects the cells of the body causing abnormal growths and may lead to
development of cancer. However, if not exposed for long, the cells can naturally repair
themselves after exposure to radioactivity

16. State Nuclear chain reaction.

Nuclear chain reactions are series of nuclear fissions (splitting of atomic nuclei), each
initiated by a neutron produced in a preceding fission. For example, 21/2 neutrons on the
average are released by the fission of each uranium-235 nucleus that absorbs a low-energy
neutron. Provided that no more than 11/2 neutrons per fission on the average are lost through
leakage and non-fission-producing capture by other nuclei, one neutron per fission on the
average remains to sustain the series. Thus the chain reaction is self-sustaining if the ratio of
the number of daughter neutrons that cause fission to the number of parent neutrons is 1 (as
in nuclear reactors) or greater than 1 (as in nuclear explosions).

17. Write the components of nuclear reactor.

1. Reactor core, 2. Reflector, 3. Pressure Vessel, 4. Shielding, 5.Heat Exchanger, 6.

Turbine, & 7. Containment

18. Mention any two differences of a nuclear reaction and a chemical reaction?
 S.No Nuclear Reaction Chemical Reaction
During nuclear reactions, the During chemical reactions, elements do not
1 nuclei of atoms undergo change lose their identity. In these reactions, only
and therefore new elements are the electrons in the outermost shell of atoms
formed as a result of such participate whereas the nuclei of atoms
reactions. remain unchanged.

2 Rate of a nuclear reaction is Chemical reactions are accompanied

independent of temperature by relatively small energy changes and
and pressure and cannot be can be reversed
reversed

19. What is breeder reactor?

Breeder reactor, nuclear reactor that produces more fissionable material than it consumes to
generate energy. This special type of reactor is designed to extend the nuclear fuel supply for
electric power generation. Whereas a conventional nuclear reactor can use only the readily
fissionable but scarce isotope uranium-235 for fuel, a breeder reactor employs either uranium-
238 or thorium, of which sizable quantities are available. Uranium-238, for example,
accounts for more than 99 percent of all naturally occurring uranium. In breeders,
approximately 70 percent of this isotope can be utilized for power production. Conventional
reactors, in contrast, can extract less than one percent of its energy

20. Name a few coolants for nuclear reactor.

Coolants : Ordinary water, Heavy water, Liquid metal ( like Sodium),Organic liquids &
gases ( like CO2)

PART – B (16 Marks)

1. State phase rule and explain the terms involved in it.

Statement
 The number of degree of freedom (F) of the system is related to number of components (C)
and number of phases (P) when they are influenced by pressure, temperature and
concentration and they are not influenced by gravity or electrical or magnetic forces at
equilibrium, then phase rule equation can be written as.

Explanation of terms
1. Phase (P)
Phase is defined as, “any homogeneous physically distinct and mechanically separable from
other parts of the system by definite boundaries”.
a. Gaseous phase
All gases are completely miscible and there is no boundary between one gas and the other.
Example
Air, which is a mixture of O2, H2, N2, CO2 and water vapour, etc., constitutes a single phase.
b. Liquid phase
The number of liquid phases depends on the number of liquid present and their miscibilities.
If two liquids are immiscible they are said to exist in two phases.
Example
Benzene-Water, Alcohol-Water
c. Solid phase
Every solid constitutes a separate phase.
Example
Decomposition of CaCO3

CaCO3(s) CaO(s) + CO2(g)

It involves three phases, solid CaCO3, solid CaO and gaseous CO2.
Consider a water system consisting of three phases.

2. Ice(s) Water(l) Vapour(g)

Each phase is physically distinct and homogeneous and there are definite boundaries between
phases. So this forms three phases.

2. Component (C)
Component is defined as, “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
equilibrium”.
Example
(i) Consider a water system consisting of three parts.

Ice(s) Water(l) Vapour(g)

The chemical composition of all three phases is H2O, but different physical form. Hence the
number of component is one.
(ii) Sulphur exists in four phases namely rhombic sulphur, monoclinic sulphur, liquid sulphur
and gaseous sulphur but the component is only sulphur i.e. single component.
(iii) Ammonium chloride dissociates into equivalent amount of ammonia gas and hydrogen
chloride gas.

NH4Cl NH3(g) + HCl(g)

Hence the number of component is only one.
(iv)A solution of NaCl in H2O can be represented as

NaCl(s) + H2O(l) NaCl(l)

The numbers of components are two.

3. Degree of freedom
It is defined as, “the minimum number of independent variable factors such as temperature,
pressure and concentration, which must be fixed in order to define the system completely”.
Example

(i) Ice(s) Water(l) Water Vapour(g)

If all the three phases are at equilibrium at a point, no degrees of freedom can be altered.
Hence the degree of freedom is zero.

(ii) Water(l) Water vapour(g)

 Here liquid water is in equilibrium with water vapour. Hence any one degrees of freedom
such as temperature or pressure has to be fixed to define the system. Therefore the degree of
freedom is one.
(iii) For defining a single system such as water, two degrees of freedom is essential. Since
water at the same temperature can exist at different pressures, both the degrees of freedom
have to be fixed for defining the system.
(iv) For gaseous phase mixture both pressure and temperature have to be fixed in defining the
system. Hence the degrees of freedom will become two.
2 Draw a neat phase diagram of water system and explain the curves, areas and points
In it ?

One Component System

One component system may be defined as the system in equilibrium which is possible to
express all phases in terms of one component.
Example: Water system
The water system is a one component system with the maximum of three phases co-existing.
Water can exist in three phases, namely solid, liquid and vapour.
Ice(s) Water(l) Water vapour(v)
(H2O) (H2O) (H2O)
In a one component system like water system the maximum degrees of freedom is only two.
Hence such systems can be graphically represented by the variables temperature in the X-axis
and pressure in the Y-axis.
The phase diagram for the water system is shown in figure.
 The above phase diagram constitute the following
(a) Areas : Below BTC - Vapour
Above ATC - Liquid
Above BAT - Solid
(b) Curves : TA - Vaporization curve
TB - Sublimation Curve
TC - methyl/freezing curve
A’T - metastable Curve.
(c) Point : Triple point – ‘T’

(i) Areas
Areas ATB, ATC and BTC represent water vapour, water and solid is respectively. Each
area represents a single phase. Appling phase rule, for the areas
F = C-P+2
=1-1+2=2
Show that the system is bivalent. Hence to define a system in the areas but the variables
pressure and temperature have to be fixed.
(ii) Curves
The curve TA vaporization curve represents the equilibrium between liquid and vapour.
Water Water vapour
The curve TB Sublimation curve
Solid Ice Water vapour
The curve TC i.e. melting curve
Ice Water
In each of these cases, these are two phases in equilibrium. Applying phase rule,
F = C-P+2
=1-2+2=1
These systems are univalent in nature. Hence to define system only one variable is
enough. It can be seen that for any given temperature these exist only one vapour pressure.
Similarly, for each vapour pressure only one temperature can be maintained.
A’T metastable curve:
Some times it is possible with due care to cool water below it freezing temperature
without the separation of ice. The water is then said to be super cooled and can be kept as such
almost indefinitely if the presence of ice (or) any other solid phase is carefully avoided.
(iii)Triple point:
These curves AT, BT and CT meet at T at which all the three phases exist in equilibrium.
Ice(S) Water(l) Water vapour(V)
Applying phase rule to this point T
F = C-P+2
=1-3+2=0
Shows that the system is non-variable the point is obtained at the temperature 0.00980C and
pressure 4.58mm. Any slight changes in Temperature (or) Pressure will cause any one of the
phases to disappear. Hence the system is invariant.

3. Draw a neat phase diagram of lead silver system and explain the curves, areas and points in
it.
Pb-Ag system
It has two component and four phases. (Solid Ag, Solid Pb, Solid solution of molten Ag-
Pb and vapour)
The boiling points of Ag and Pb are high and the vapour phase is absent. So it has 3
phases. So pressure has no effect on the system and we have to consider T and composition are
shown in figure.

Areas
(a) Above ACB (b) Below AC (c) Below BC
Above ACB
This region is single phase system, the solution of molten Ag and Pb
F=C-P+2
=2-1+1=2
Thus the system solution Ag/Pb is bivalent i.e for representing any point in this region
two variables have to be fixed.
Below AC
Represents the phase Ag + solution
Below BC
The phases Pb + solution. The area below the temperature 303ºC represents eutectic +
solid Ag and Eutectic + Solid Pb.
 All these areas have two phases and one degree of freedom
F = C-P+1
=2-2+1=1
Curves
(i) 2 curves AC and BC
(ii) Eutectic point C
Curve AC
Freezing point curve of Ag
A represent melting point of solid (9610C) and the curve AC shows that the addition of
Pb lowers the melting point along it. The phases of equilibrium along AC are solid Ag and
solution of Ag and Pb.
Curve BC: (Freezing point curve of Pb)
B represents the melting point of Pb and BC shows that the melting point is lowered by
the addition of Ag.
The Curves AC and BC are the equilibrium curves of pure liquid melt with solid silver
and the pure liquid melt with solid lead respectively.
F = C-P+1
=2-2+1=1
The system along the curves is univariant.
Eutectic point C
The curves AC and BC reach upto the lowest point C (3030C). This point is called as
eutectic point C. where the solution gets saturated with maximum amount of lead (97.4%) and
silver (2.6%).This mixture is known as eutectic mixture and the temperature 3030C is known as
eutectic temperature. Here solid Ag, Solid Pb and solid solution are in equilibrium. Applying
reduced phase rule
F = C-P+1
=2-3+1=0
Thus the system Ag/Pb at C is non-variant ‘ie’ both the variables T and composition are
fixed. It we raise the temperature above the Eutectic temperature, the solid phases Ag and Pb
disappear and if we cool below it, the metal and the Eutectic solidify and solution phases does
not exists.
4. With suitable examples explain the terms phase, component and degree of freedom.

1. Phase (P)
Phase is defined as, “any homogeneous physically distinct and mechanically separable from
other parts of the system by definite boundaries”.
a. Gaseous phase
All gases are completely miscible and there is no boundary between one gas and the other.
Example
Air, which is a mixture of O2, H2, N2, CO2 and water vapour, etc., constitutes a single phase.
b. Liquid phase
The number of liquid phases depends on the number of liquid present and their miscibilities.
If two liquids are immiscible they are said to exist in two phases.
Example
Benzene-Water, Alcohol-Water
c. Solid phase
Every solid constitutes a separate phase.
Example
Decomposition of CaCO3

CaCO3(s) CaO(s) + CO2(g)

It involves three phases, solid CaCO3, solid CaO and gaseous CO2.
Consider a water system consisting of three phases.

5. Ice(s) Water(l) Vapour(g)

Each phase is physically distinct and homogeneous and there are definite boundaries between
phases. So this forms three phases.

2. Component (C)
Component is defined as, “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
equilibrium”.
Example
(i) Consider a water system consisting of three parts.
Ice(s) Water(l) Vapour(g)
The chemical composition of all three phases is H2O, but different physical form. Hence the
number of component is one.
(ii) Sulphur exists in four phases namely rhombic sulphur, monoclinic sulphur, liquid sulphur
and gaseous sulphur but the component is only sulphur i.e. single component.
(iii) Ammonium chloride dissociates into equivalent amount of ammonia gas and hydrogen
chloride gas.

NH4Cl NH3(g) + HCl(g)

Hence the number of component is only one.
(iv)A solution of NaCl in H2O can be represented as

NaCl(s) + H2O(l) NaCl(l)

The numbers of components are two.

3. Degree of freedom
It is defined as, “the minimum number of independent variable factors such as temperature,
pressure and concentration, which must be fixed in order to define the system completely”.
Example

(i) Ice(s) Water(l) Water Vapour(g)

If all the three phases are at equilibrium at a point, no degrees of freedom can be altered.
Hence the degree of freedom is zero.

(ii) Water(l) Water vapour(g)

Here liquid water is in equilibrium with water vapour. Hence any one degrees of freedom
such as temperature or pressure has to be fixed to define the system. Therefore the degree of
freedom is one.
(iii) For defining a single system such as water, two degrees of freedom is essential. Since
water at the same temperature can exist at different pressures, both the degrees of freedom
have to be fixed for defining the system.
(iv) For gaseous phase mixture both pressure and temperature have to be fixed in defining the
system. Hence the degrees of freedom will become two.
5. What is meant by phase diagram? With the help of the phase diagram, explain triple point and
eutectic point.

One component system may be defined as the system in equilibrium which is possible to express
all phases in terms of one component.
Example: Water system
The water system is a one component system with the maximum of three phases co-
existing.
Water can exist in three phases, namely solid, liquid and vapour.
Ice(s) Water(l) Water vapour(v)
(H2O) (H2O) (H2O)
In a one component system like water system the maximum degrees of freedom is only
two. Hence such systems can be graphically represented by the variables temperature in the X-
axis and pressure in the Y-axis.
The phase diagram for the water system is shown in figure.

The above phase diagram constitute the following

(a) Areas : Below BTC - Vapour
Above ATC - Liquid
 Above BAT - Solid
(b) Curves : TA - Vaporization curve
TB - Sublimation Curve
TC - methyl/freezing curve
A’T - metastable Curve.
(c) Point : Triple point – ‘T’
Triple point:
These curves AT, BT and CT meet at T at which all the three phases exist in equilibrium.
Ice(S) Water(l) Water vapour(V)
Applying phase rule to this point T
F = C-P+2
=1-3+2=0
Shows that the system is non-variable the point is obtained at the temperature 0.00980C and
pressure 4.58mm. Any slight changes in Temperature (or) Pressure will cause any one of the
phases to disappear. Hence the system is invariant.
Simple Eutectic System
Two substances which are completely miscible in the liquid state but not miscible in the
solid state is a Simple Eutectic system.
Eg: Zn-Cd system and Pb-Ag system
Pb-Ag system
It has two component and four phases. (Solid Ag, Solid Pb, Solid solution of molten Ag-
Pb and vapour)
The boiling points of Ag and Pb are high and the vapour phase is absent. So it has 3
phases. So pressure has no effect on the system and we have to consider T and composition are
shown in figure.
Areas
(a) Above ACB (b) Below AC (c) Below BC
Curves
(i) 2 curves AC and BC
(ii) Eutectic point C
Curve AC
Freezing point curve of Ag
A represent melting point of solid (9610C) and the curve AC shows that the addition of
Pb lowers the melting point along it. The phases of equilibrium along AC are solid Ag and
solution of Ag and Pb.
Curve BC: (Freezing point curve of Pb)
B represents the melting point of Pb and BC shows that the melting point is lowered by
the addition of Ag.
The Curves AC and BC are the equilibrium curves of pure liquid melt with solid silver
and the pure liquid melt with solid lead respectively.
F = C-P+1
=2-2+1=1
The system along the curves is univariant.
Eutectic point C
 The curves AC and BC reach upto the lowest point C (3030C). This point is called as
eutectic point C. where the solution gets saturated with maximum amount of lead (97.4%) and
silver (2.6%).This mixture is known as eutectic mixture and the temperature 3030C is known as
eutectic temperature. Here solid Ag, Solid Pb and solid solution are in equilibrium. Applying
reduced phase rule
F = C-P+1
=2-3+1=0
Thus the system Ag/Pb at C is non-variant ‘ie’ both the variables T and composition are
fixed. It we raise the temperature above the Eutectic temperature, the solid phases Ag and Pb
disappear and if we cool below it, the metal and the Eutectic solidify and solution phases does
not exists.

6. Define nuclear chain reaction? Explain the basic principles and characteristics of it.

Nuclear Reactions
The reactions considered so far occur spontaneously, and involve a conversion of mass
into (mainly) kinetic energy of the decay products. There is another class of nuclear reactions
which can be induced, an example of which is bombarding a nitrogen nucleus with an alpha
particle:
4
2He + 147N 17
8O + 11H

Types of Nuclear Reactions

i) Nuclear fusion

ii) Nuclear fission

Nuclear Fusion

Nuclear fusion is a nuclear reaction in which two light nuclei combine to form heavier
nuclei with the simultaneous release of energy.
 1
1 H + 11 H 2
1 H + 01 e + .

Fusion reactions are the main source of energy for the sun, and are also used in certain
types of nuclear weapons.

Nuclear Fission

Nuclear fission is the process of splitting of a heavy nucleus into two approximately
equal parts, with simultaneous liberation of a huge amount of energy. Example - fission of U-
235 by neutrons.

1
0 n + 23592 U 140
56 Ba + 9336 Kr + 3 10 n + energy.

An interesting feature of this neutron-induced reaction is the presence of neutrons in the

products. It turns out that the initial kinetic energy of the reacting neutrons can be relatively
small, and the released neutrons can induce reactions in nearby Uranium atoms. Such a chain
reaction has important consequences in the design of nuclear reactors, as well as nuclear
weapons.

The typical energies involved in nuclear reactions are of the order of MeV ( 10 6 eV),
compared to the eV scale of chemical reactions.

Nuclear reactors are used as a source of power in large power grids and in submarines.
Over 16% of the world's electricity is produced from nuclear energy, more than from all sources.

7. Explain nuclear power plant with a neat sketch.

Nuclear Reactor
A device used to generate power, in which nuclear fission takes place at a diluted and
controlled rate, so that the energy librated can be utilized for peaceful purposes like like
generation of electricity.
Principle
 The energy released from continuous fission of the atoms of the fuel is harnessed as heat
in either a gas or water, and is used to produce steam. The steam is used to drive the turbines
which produce electricity.

Components of a Nuclear Reactor

There are several components common to most types of reactors:

1. Reactor core

It is the part of a nuclear power plant, where controlled fission reaction is made to occur
and where heat energy is librated. It consists of an assemblage of fuel elements, control rods,
coolant and moderator. It generally has a shape approximating a circular cylinder with diameter
ranging from 5 to 15 m.

(i) Fuel: The nuclear fuels generally used in the reactor are (a) natural uranium (99.28%
-238 and 0.714% U-235) (b) enriched uranium (containing higher percentage of U-
235) (c) U-235 obtained in the clear reactors during fission of Th-232 (d) Pu- 239
obtained from U-238.
(ii) Moderator: Material in the core which slows down the neutrons released from fission
so that they cause more fission. It is usually water, but may be heavy water or
graphite.
 (iii) Coolants: A fluid circulating through the core so as to transfer the heat from it. These
are to rehe reactor move the intense heat produced in the reactor and to bring it out
for utilization. Important coolants are ordinary water, heavy water liquid metal (like
sodium), organic liquids and gases (like carbon dioxide).
(iv) Control rods: These are made with neutron-absorbing material such as cadmium,
hafnium or boron, and are inserted or withdrawn from the core to control the rate of
reaction, or to halt it. It has several purposes:

(a) for start up i.e., to bring the reactor up to its normal operating level
(b) for maintaining it at normal level i.e. to keep power production t a steady state
(c) for shutting the reactor under normal or emergency conditions
(d) to prevent the chain reaction from becoming violent and consequently, avoiding the
damage of the reactor.

2. Reflector

Reflector is usually place around the core to reflect back some of the neutrons that leak
out from the surface of the core. The required properties of a good reflector are low
absorption and high reflection for neutrons, High resistance to oxidation and irradiation as
well as high radiation stability. Reflector is generally, made up of the same material as the
moderator (H2O, D2O and graphite)

3.Pressure vessel

Pressure vessel encloses the core and the reflector. It also provides the entrance and exit
passages for coolant. Pressure vessel has to withstand the pressure as high as 200kg/cm2.
The holes at the top of the vessel are also provided to insert or pull out the control rods.

4. Shielding

Its purpose is to attenciate (i.e., weaken) the γ- rays and other radiations coming from the
reactor, so that there is no hazard to persons in immediate vicinity. To prevent the effect of these
harmful radiations on the human beings, it is necessary to absorb them, Neutrons, γ- rays and
also other radiations are effectively absorbed by the concret and steel. In a high power reactor,
there are two shields:

(a) “Thermal shield” is very close to reactor core and consists of 50 to 60 cm thick
iron or steel covering. By absorbing most of the γ- rays, it becomes heated and
prevents the adjacent wall of the pressure vessel from becoming hot. This thermal
shield is cooled by the circulation of water.
(b) “Biological shield” is a layer of concrete, few decimeters thick and it surrounds
the thermal shield. Its function is to absorb any γ- rays and neutrons coming out
from the inner thermal shield.

5. Heat exchanger

Heat exchanger transfers the heat liberated from the reactor core to boil water and get
steam at about 400kg/cm2.

6. Turbine

The steam at high pressure, generated in the heat exchanger, is used to operate a steam
turbine, which drives a generator to produce electricity. The exhaust stem is condensed and sent
back to the heat exchanger.

7. Containment

The structure around the reactor and associated steam generators which is designed to
protect it from outside intrusion and to protect those outside from the effects of radiation in case
of any serious malfunction inside. It is typically a metre-thick concrete and steel structure.

8. Explain the significance and working principles of breeder reactor with necessary equations
and sketch.
 A breeder reactor is a nuclear reactor capable of generating more fissile material than it
consumes.[1] These devices are able to achieve this feat because their neutron economy is high
enough to breed more fissile fuel than they use from fertile material like uranium-238 or
thorium-232. Breeders were at first considered attractive because of their superior fuel
economy compared to light water reactors.

Schematic diagram showing the difference between the Loop and Pool types of LMFBR.

As of 2006, all large-scale fast breeder reactor (FBR) power stations have been liquid metal fast
breeder reactors (LMFBR) cooled by liquid sodium. These have been of one of two designs:[1]

 Loop type, in which the primary coolant is circulated through primary heat exchangers
outside the reactor tank (but inside the biological shield due to radioactive sodium-24 in
the primary coolant)
 Pool type, in which the primary heat exchangers and pumps are immersed in the reactor
tank

All current fast neutron reactor designs use liquid metal as the primary coolant, to transfer heat
from the core to steam used to power the electricity generating turbines. FBRs have been built
cooled by liquid metals other than sodium—some early FBRs used mercury, other experimental
reactors have used a sodium-potassium alloy called NaK. Both have the advantage that they are
liquids at room temperature, which is convenient for experimental rigs but less important for
pilot or full scale power stations. Lead and lead-bismuth alloy have also been used. The relative
merits of lead vs sodium are discussed here. Looking further ahead, three of the proposed
generation IV reactor types are FBRs:[35]

 Gas-Cooled Fast Reactor (GFR) cooled by helium.

 Sodium-Cooled Fast Reactor (SFR) based on the existing Liquid Metal FBR (LMFBR)
and Integral Fast Reactor designs.
 Lead-Cooled Fast Reactor (LFR) based on Soviet naval propulsion units.

FBRs usually use a mixed oxide fuel core of up to 20% plutonium dioxide (PuO2) and at least
80% uranium dioxide (UO2). Another fuel option is metal alloys, typically a blend of uranium,
plutonium, and zirconium (used because it is "transparent" to neutrons). Enriched uranium can
also be used on its own.

In many designs, the core is surrounded in a blanket of tubes containing non-fissile uranium-238
which, by capturing fast neutrons from the reaction in the core, is converted to fissile plutonium-
239 (as is some of the uranium in the core), which is then reprocessed and used as nuclear fuel.
Other FBR designs rely on the geometry of the fuel itself (which also contains uranium-238),
arranged to attain sufficient fast neutron capture. The plutonium-239 (or the fissile uranium-235)
fission cross-section is much smaller in a fast spectrum than in a thermal spectrum, as is the ratio
between the 239Pu/235U fission cross-section and the 238U absorption cross-section. This increases
the concentration of 239Pu/235U needed to sustain a chain reaction, as well as the ratio of breeding
to fission.

On the other hand, a fast reactor needs no moderator to slow down the neutrons at all, taking
advantage of the fast neutrons producing a greater number of neutrons per fission than slow
neutrons. For this reason ordinary liquid water, being a moderator as well as a neutron absorber,
is an undesirable primary coolant for fast reactors. Because large amounts of water in the core
are required to cool the reactor, the yield of neutrons and therefore breeding of 239Pu are strongly
affected. Theoretical work has been done on reduced moderation water reactors, which may have
a sufficiently fast spectrum to provide a breeding ratio slightly over 1. This would likely result in
an unacceptable power de rating and high costs in an liquid-water-cooled reactor, but the
supercritical water coolant of the SCWR has sufficient heat capacity to allow adequate cooling
with less water, making a fast-spectrum water-cooled reactor a practical possibility.

9. Write short note on i. Nuclear fusion ii. Nuclear fission iii. Nuclear chain reaction.

Nuclear Fusion
Nuclear fusion is a nuclear reaction in which two light nuclei combine to form heavier nuclei
with the simultaneous release of energy.

1
1 H + 11 H 2
1 H + 01 e + .

Fusion reactions are the main source of energy for the sun, and are also used in certain
types of nuclear weapons.

Nuclear Fission

Nuclear fission is the process of splitting of a heavy nucleus into two approximately
equal parts, with simultaneous liberation of a huge amount of energy. Example - fission of U-
235 by neutrons.

1
0 n + 23592 U 140
56 Ba + 9336 Kr + 3 10 n + energy.

An interesting feature of this neutron-induced reaction is the presence of neutrons in the

products. It turns out that the initial kinetic energy of the reacting neutrons can be relatively
small, and the released neutrons can induce reactions in nearby Uranium atoms. Such a chain
reaction has important consequences in the design of nuclear reactors, as well as nuclear
weapons.

The typical energies involved in nuclear reactions are of the order of MeV ( 10 6 eV),
compared to the eV scale of chemical reactions.

Nuclear reactors are used as a source of power in large power grids and in submarines.
Over 16% of the world's electricity is produced from nuclear energy, more than from all sources.

Nuclear chain reaction.

Nuclear chain reactions are series of nuclear fissions (splitting of atomic nuclei), each
initiated by a neutron produced in a preceding fission. For example, 21/2 neutrons on the
average are released by the fission of each uranium-235 nucleus that absorbs a low-energy
 neutron. Provided that no more than 11/2 neutrons per fission on the average are lost through
leakage and non-fission-producing capture by other nuclei, one neutron per fission on the
average remains to sustain the series. Thus the chain reaction is self-sustaining if the ratio of
the number of daughter neutrons that cause fission to the number of parent neutrons is 1 (as
in nuclear reactors) or greater than 1 (as in nuclear explosions).

10. Write an essay about radioactive isotopes.

ISOTOPES
An isotope is one of two or more species of atoms of a chemical element with the same
atomic number (same number or protons in the nucleus) and position in the periodic
table and nearly identical chemical behavior but with different atomic masses and
physical properties. Every chemical element has one or more isotopes.

An atom is first identified and labeled according to the number of protons in its nucleus.
This atomic number is ordinarily given the symbol Z. The great importance of the
atomic number derives from the observation that all atoms with the same atomic
number have nearly, if not precisely, identical chemical properties. A large collection of
atoms with the same atomic number constitutes a sample of an element. A bar of pure
uranium, for instance, would consist entirely of atoms with atomic number 92. The
periodic table of the elements assigns one place to every atomic number, and each of
these places is labeled with the common name of the element, as, for example, calcium,
radon, or uranium.

Not all the atoms of an element need have the same number of neutrons in their nuclei.
In fact, it is precisely the variation in the number of neutrons in the nuclei of atoms that
gives rise to isotopes. Hydrogen is a case in point. It has the atomic number 1. Three
nuclei with one proton are known that contain 0, 1, and 2 neutrons, respectively. The
three share the place in the periodic table assigned to atomic number 1 and hence are
called isotopes (from the Greek isos, meaning "same," and topos, signifying "place") of
hydrogen.

Many important properties of an isotope depend on its mass. The total number of
neutrons and protons (symbol A), or mass number, of the nucleus gives approximately
the mass measured on the so-called atomic- mass-unit (amu) scale. The numerical
difference between the actual measured mass of an isotope and A is called the mass
defect.

The specification of Z, A, and the chemical symbol (a one- or two-letter abbreviation of

the element's name, say Sy) in the form A/ZSy identifies an isotope adequately for most
purposes. Thus in the standard notation, 1/1H refers to the simplest isotope of hydrogen
and 235/92U to an isotope of uranium widely used for nuclear power generation and
nuclear weapons fabrication. (Authors who do not wish to use symbols sometimes write
out the element name and mass number‹hydrogen-1 and uranium-235 in the examples
above.)

STABLE AND UNSTABLE ISOTOPES

Isotopes utilized in nuclear medicine fall into two broad categories: Stable and
Unstable. Stable isotopes do not undergo radioactive decay.

WHAT IS A STABLE ISOTOPE?

A "stable isotope" is any of two or more forms of an element whos nuclei contains the
same number of protons and electrons, but a different number of neutrons. Stable
isotopes remain unchanged indefinitely, but "unstable" (radioactive) isotopes undergo
spontaneous disintegration. An "isotopically labeled compound" has one or more of its
atoms enriched in an isotope.

APPLICATIONS
Stable isotopes are tools used by researchers worldwide in the diagnosis of disease, to
understand metabolic pathways in humans, and to answer fundamental questions in
nature. They help researchers find answers by allowing them to look at a problem in a
new way, from a different perspective. They help to better understand a process, trace a
compound from a particular source, measure the concentration of a chemical in a
sample, or measure the rate of a related process. Stable isotopes already play an
important role in research today and will become even more important to research in
the future.

Examples of stable elements used in nuclear medicine isotopes such as carbon-13,

nitrogen-15 and oxygen-18 as well as noble gas isotopes. Uses of stable isotopes
include the custom synthesis of new and complex labeled compounds to use in
agriculture, biology, chemistry, drug testing, geology, health, nutrition, physics as well
as diagnostic techniques in medicine.
» View Examples of Stable Isotope Compounds

RADIOISOTOPES
Many of the chemical elements have a number of isotopes. The isotopes of an element
have the same number of protons in their atoms (atomic number) but different masses
due to different numbers of neutrons. In an atom in the neutral state, the number of
external electrons also equals the atomic number. These electrons determine the
chemistry of the atom. The atomic mass is the sum of the protons and neutrons. There
are 82 stable elements and about 275 stable isotopes of these elements.

When a combination of neutrons and protons, which does not already exist in nature, is
produced artificially, the atom will be unstable and is called a radioactive isotope or
radioisotope. There are also a number of unstable natural isotopes arising from the
decay of primordial uranium and thorium.

Overall there are some 3800 radioisotopes. At present there are up to 200 radioisotopes
used on a regular basis, and most must be produced artificially.

Radioisotopes can be manufactured in several ways. The most common is by neutron

activation in a nuclear reactor. This involves the capture of a neutron by the nucleus of
an atom resulting in an excess of neutrons (neutron rich). Some radioisotopes are
manufactured in a cyclotron in which protons are introduced to the nucleus resulting in
a deficiency of neutrons (proton rich).

The nucleus of a radioisotope usually becomes stable by emitting an alpha and/or beta
particle (or positron). These particles may be accompanied by the emission of energy in
the form of electromagnetic radiation known as gamma rays. This process is known as
radioactive decay. Radioactive products which are used in medicine are referred to as
radiopharmaceuticals.

NUCLEAR MEDICINE
This is a branch of medicine that uses radiation to provide information about the
functioning of a person's specific organs or to treat disease. In most cases, the
information is used by physicians to make a quick, accurate diagnosis of the patient's
illness. The thyroid, bones, heart, liver and many other organs can be easily imaged,
and disorders in their function revealed. In some cases radiation can be used to treat
diseased organs, or tumors.

In developed countries (26% of world population) the frequency of diagnostic nuclear

medicine is 1.9% per year, and the frequency of therapy with radioisotopes is about one
tenth of this.

Nuclear medicine was developed in the 1950s by physicians with an endocrine

emphasis, initially using iodine-131 to diagnose and then treat thyroid disease. In
recent years specialists have also come from radiology, as dual CT/PET procedures
have become established.

DIAGNOSIS
Diagnostic techniques in nuclear medicine use radioactive tracers which emit gamma
rays from within the body. These tracers are generally short- lived isotopes linked to
chemical compounds which permit specific physiological processes to be scrutinised.
They can be given by injection, inhalation or orally. The first type are where single
photons are detected by a gamma camera which can view organs from many different
angles. The camera builds up an image from the points from which radiation is emitted;
this image is enhanced by a computer and viewed by a physician on a monitor for
indications of abnormal conditions.

A more recent development is Positron Emission Tomography (PET) which is a more

precise and sophisticated technique using isotopes produced in a cyclotron. A positron-
emitting radionuclide is introduced, usually by injection, and accumulates in the target
tissue. As it decays it emits a positron, which promptly combines with a nearby
electron resulting in the simultaneous emission of two identifiable gamma rays in
opposite directions. These are detected by a PET camera and give very precise
indication of their origin. PET's most important clinical role is in oncology, with
fluorine-18 as the tracer, since it has proven to be the most accurate non-invasive
method of detecting and evaluating most cancers. It is also well used in cardiac and
brain imaging.

New procedures combine PET with CT scans to give co-registration of the two images,
enabling 30% better diagnosis than with traditional gamma camera alone.

Positioning of the radiation source within the body makes the fundamental difference
between nuclear medicine imaging and other imaging techniques such as x-rays.
Gamma imaging by either method described provides a view of the position and
concentration of the radioisotope within the body. Organ malfunction can be indicated
if the isotope is either partially taken up in the organ (cold spot), or taken up in excess
(hot spot). If a series of images is taken over a period of time, an unusual pattern or rate
of isotope movement could indicate malfunction in the organ.

A distinct advantage of nuclear imaging over x-ray techniques is that both bone and
soft tissue can be imaged very successfully. This has led to its common use in
developed countries where the probability of anyone having such a test is about one in
two and rising. The mean effective dose is 4.6 mSv per diagnostic procedure.

RADIOTHERAPY
Rapidly dividing cells are particularly sensitive to damage by radiation. For this reason,
some cancerous growths can be controlled or eliminated by irradiating the area
containing the growth. External irradiation can be carried out using a gamma beam
from a radioactive cobalt-60 source, though in developed countries the much more
versatile linear accelerators are now being utilised as a high-energy x-ray source
(gamma and x-rays are much the same).

Internal radiotherapy is by administering or planting a small radiation source, usually a

gamma or beta emitter, in the target area. Iodine-131 is commonly used to treat thyroid
cancer, probably the most successful kind of cancer treatment. It is also used to treat
non-malignant thyroid disorders. Iridium-192 implants are used especially in the head
and breast. They are produced in wire form and are introduced through a catheter to the
target area. After administering the correct dose, the implant wire is removed to
shielded storage. This brachytherapy (short-range) procedure gives less overall
radiation to the body, is more localised to the target tumour and is cost effective.

Treating leukaemia may involve a bone marrow transplant, in which case the defective
bone marrow will first be killed off with a massive (and otherwise lethal) dose of
radiation before being replaced with healthy bone marrow from a donor.
Many therapeutic procedures are palliative, usually to relieve pain. For instance,
strontium-89 and (increasingly) samarium 153 are used for the relief of cancer-induced
bone pain. Rhenium-186 is a newer product for this.

A new field is targeted alpha therapy (TAT), especially for the control of dispersed
cancers. The short range of very energetic alpha emissions in tissue means that a large
fraction of that radiative energy goes into the targeted cancer cells, once a carrier has
taken the alpha-emitting radionuclide to exactly the right place. Laboratory studies are
encouraging and clinical trials for leukaemia, cystic glioma and melanoma are under
way.

An experimental development of this is neutron capture therapy using boron-10 which

concentrates in malignant brain tumours. The patient is then irradiated with thermal
neutrons which are strongly absorbed by the boron, producing high-energy alpha
particles which kill the cancer. This requires the patient to be brought to a nuclear
reactor, rather than the radioisotopes being taken to the patient.

With any therapeutic procedure the aim is to confine the radiation to well- defined
target volumes of the patient. The doses per therapeutic procedure are typically 20-60
Gy.

BIOCHEMICAL ANALYSIS
It is very easy to detect the presence or absence of some radioactive materials even
when they exist in very low concentrations. Radioisotopes can therefore be used to
label molecules of biological samples in vitro (out of the body). Pathologists have
devised hundreds of tests to determine the constituents of blood, serum, urine,
hormones, antigens and many drugs by means of associated radioisotopes. These
procedures are known as radioimmuno assays and, although the biochemistry is
complex, kits manufactured for laboratory use are very easy to use and give accurate
results.

DIAGNOSTIC RADIOPHARMACEUTICALS
Every organ in our bodies acts differently from a chemical point of view. Doctors and
chemists have identified a number of chemicals which are absorbed by specific organs.
The thyroid, for example, takes up iodine, the brain consumes quantities of glucose,
and so on. With this knowledge, radiopharmacists are able to attach various
radioisotopes to biologically active substances. Once a radioactive form of one of these
substances enters the body, it is incorporated into the normal biological processes and
excreted in the usual ways.

Diagnostic radiopharmaceuticals can be used to examine blood flow to the brain,

functioning of the liver, lungs, heart or kidneys, to assess bone growth, and to confirm
other diagnostic procedures. Another important use is to predict the effects of surgery
and assess changes since treatment. The amount of the radiopharmaceutical given to a
patient is just sufficient to obtain the required information before its decay. The
radiation dose received is medically insignificant. The patient experiences no
discomfort during the test and after a short time there is no trace that the test was ever
done. The non-invasive nature of this technology, together with the ability to observe
an organ functioning from outside the body, makes this technique a powerful
diagnostic tool.

A radioisotope used for diagnosis must emit gamma rays of sufficient energy to escape
from the body and it must have a half-life short enough for it to decay away soon after
imaging is completed.

The radioisotope most widely used in medicine is technetium-99m, employed in some

80% of all nuclear medicine procedures. It is an isotope of the artificially-produced
element technetium and it has almost ideal characteristics for a nuclear medicine scan.
These are: It has a half-life of six hours which is long enough to examine metabolic
processes yet short enough to minimise the radiation dose to the patient. Technetium-
99m decays by a process called "isomeric"; which emits gamma rays and low energy
electrons. Since there is no high energy beta emission the radiation dose to the patient
is low.

The low energy gamma rays it emits easily escape the human body and are accurately
detected by a gamma camera. Once again the radiation dose to the patient is
minimized.

The chemistry of technetium is so versatile it can form tracers by being incorporated

into a range of biologically-active substances to ensure that it concentrates in the tissue
or organ of interest.

Its logistics also favour its use. Technetium generators, a lead pot enclosing a glass
tube containing the radioisotope, are supplied to hospitals from the nuclear reactor
where the isotopes are made. They contain molybdenum-99, with a half-life of 66
hours, which progressively decays to technetium-99. The Tc-99 is washed out of the
lead pot by saline solution when it is required. After two weeks or less the generator is
returned for recharging.

A similar generator system is used to produce rubidium-82 for PET imaging from
strontium-82 - which has a half-life of 25 days. Myocardial Perfusion Imaging (MPI)
uses thallium-201 chloride or technetium-99m and is important for detection and
prognosis of coronary artery disease.

For PET imaging, the main radiopharmaceutical is Fluoro-deoxy glucose (FDG)

incorporating F-18 - with a half-life of just under two hours, as a tracer. The FDG is
readily incorporated into the cell without being broken down, and is a good indicator of
cell metabolism.

In diagnostic medicine, there is a strong trend to using more cyclotron- produced

 isotopes such as F-18 as PET and CT/PET become more widely available. However,
the procedure needs to be undertaken within two hours of a cyclotron.

Unit –V- CHROMATOGRAPHY AND SPECTROSCOPY

PART –A (2 Marks)
1. What is atomic spectroscopy?
Atomic spectrascopy is concerned with the interaction of electromagnetic radiation with
atoms. In atomic spectra, the transition takes place from one electronic energy state to
another (i.e.) between the atomic energy levels.

2. What is molecular spectroscopy?

Molecular spectrascopy is concerned with the interaction of electromagnetic radiation with
molecules. In molecular spectra involves the transition between rotational and vibrational
energy levels in addition to electronic transitions.

3. What are absorption and emission spectrums?

Absorption spectrum: When there is a transition from a state of lower energy to a state of
higher energy, the energy absorbed will be equal to the energy difference, ∆E = hυ. The
spectrum recorded will be absorption spectrum.
Emission spectrum: When there is a transition from a state of lower energy to a state of
higher energy, the energy emitted will be equal to the energy difference, ∆E = hυ. The
spectrum recorded will be emission spectrum.

4. State Beer-Lambert’s law.

The intensity of a beam of monochromator light decreases exponentially as the concentration
of the absorbing substance in solution increases. This statement is known as Beer’s law
The absorbance (A) is directly proportional to the molar concentration(C) as well as path
length of the medium (l).
A = Cl
  is the molar absorptivity coefficient
C is the concentration of solution
l is the path length of the medium

5. State the principle of UV-visible spectroscopy?

It arises from the transition of valence electrons with in the molecule or ion from the lower
electronic level to higher electronic level. This transition occurs due to absorption of UV
(100 – 400 nm) or Visbile (400 – 750nm) region of the electronic spectrum by a molecule or
ion.
E1 – Eo = hυ

6. What are chromophores and auxochrome?

Chromophores: The presence of one or more unsaturated linkages in a compound is
responsible for the colour of the compound, is called as Chromophores.
Eg: -C C- , -C N
Auxochromes: An atom or group of atoms which does not give rise to absorption band on its
own, but when conjugate to chromophore will cause a red shift.
Eg: -OH, -NH2

7. What are stretching and bending vibrations?

Stretching vibration: During stretching, the distance between two atoms decreases or
increases, but bond-angle remains un-altered.
Bending vibration: During bending, the bond-angle decreases or increases, but bond-distance
remains un-altered.

8. What is the electromagnetic radiation?

It is a form of energy that is transmitted through space at an enormous velocity. The common
example of electromagnetic radiation is visible light. It has a dual character like wave as well
as particle behavior.
9. What are the various types of electronic transitions?
n → Π*, σ → σ*, n → σ*, Π → Π*
10. Give the frequency region of Infrared spectrum?
The range in the electromagnetic spectrum extending from 12500 to 50 cm-1 is commonly
reefed to as the infrared. This region is further divided into three sub regions.
Near IR: 12500 to 4000 cm-1
Ordinary IR: 4000 to 667 cm-1
Far IR: 667 to 50 cm-1
11. Write any two advantages of AAS.
 a. AAS is rapid and accurate method, using which nearly 70 – 80 metals can be
determined from any sample.
b. Vanadium is lubricating oils can be estimated.
c. This technique is also used in steel, metal, pharmaceutical and food industry.
12. What are the components of UV Visible spectrophotometry?
Radiation source, Monochromators, Cells, Detectors, Recording system.
13. Define eluent
It is a solvent used to carry the components of a mixture through a stationary phase.
14. State (i) Solvent (ii) Solute (iii) Solution
Solvent: A solvent is a substance which dissolves a solute
Solute: A solute is a substance which dissolved in solvent
Solution: It is a homogeneous mixture of solute and solvent.
15. Define Chromatogram.
A chromatogram is the visual output of the chromatograph. In the case of an optimal
separation, different peaks or patterns on the chromatogram correspond to different
components of the separated mixture. The graph is plotted on the x-axis is the retention time
and plotted on the y-axis a signal corresponding to the response created by the analytes
exiting the system. In the case of an optimal system the signal is proportional to the
concentration of the specific analyte separated.
16. State Rf factor.
It is defined as the ratio of the distance travelled by the substance to the distance travelled by
the solvent.
17. State Retention time.
It is the time between injection of a sample and the appearance of a solute peak at the
detector.
18. Why TLC is better than Paper chromatography.
Compared to paper, it has the advantage of faster runs, better separations, and the choice
between different adsorbents.
19. What are the types of gas chromatography? How it is classified?
There are two types of gas chromatography.
 a. If the stationary phase is solid, adsorption takes place. It is called gas solid
chromatography.
b. If the stationary phase is liquid, partition takes place. It is called gas liquid
chromatography.

20. What is elution?

It is a process of recovering various substances from the chromatogram is called elution. The
solvent used for elution is called eluent.

PART –B (16 Marks)

1. Write the principle involved in Column chromatography.

PRINCIPLE

Column chromatography is a separation technique in which the stationary phase is within

a tube. The particles of the solid stationary phase or the support coated with a liquid stationary
phase may fill the whole inside volume of the tube (packed column) or be concentrated on or
along the inside tube wall. It is leaving an open, unrestricted path for the mobile phase in the
middle part of the tube (open tubular column). Differences in rates of movement through the
medium are calculated to different retention times of the sample.

METHOD

The classical preparative chromatography column is a glass tube with a diameter from
5 mm to 50 mm and a height of 5 cm to 1 m with a tap and some kind of a filter (a glass frit or
glass wool plug – to prevent the loss of the stationary phase) at the bottom. Two methods are
generally used to prepare a column: the dry method, and the wet method.
 For the dry method, the column is first filled with dry stationary phase powder, followed
by the addition of mobile phase, which is flushed through the column until it is completely wet,
and from this point is never allowed to run dry.

For the wet method, slurry of the eluent is prepared with the stationary phase powder and
then carefully poured into the column. Care must be taken to avoid air bubbles. A solution of the
organic material is pipetted on top of the stationary phase. This layer is usually topped with a
small layer of sand or with cotton or glass wool to protect the shape of the organic layer from the
velocity of newly added eluent. Eluent is slowly passed through the column to advance the
organic material. Often a spherical eluent reservoir or an eluent-filled and stoppered separating
funnel is put on top of the column.

APPLICATIONS

 Column chromatography is used to purify individual chemical compounds from mixtures

of compounds.
 It is often used for preparative applications on scales from micrograms up to kilo.
 The main advantage of column chromatography is the relatively low cost and
disposability of the stationary phase used in the process. The latter prevents cross-
contamination and stationary phase degradation due to recycling.

2. Give brief note on (i) TLC (ii) Paper chromatography

. THIN LAYER CHROMATOGRAPHY (TLC)

PRINCIPLE

Thin layer chromatography (TLC) is a widely employed laboratory technique and is

similar to paper chromatography. However, instead of using a stationary phase of paper, it
involves a stationary phase of a thin layer of adsorbent like silica gel, alumina, or cellulose on a
flat, inert substrate. Compared to paper, it has the advantage of faster runs, better separations,
and the choice between different adsorbents. For even better resolution and to allow for
quantification, high-performance TLC can be used.

METHOD

 A small spot of solution containing the sample is applied to TLC plate about 1.5
centimeters from the bottom edge. The solvent is allowed to completely evaporate off,
otherwise a very poor or no separation will be achieved. If a non-volatile solvent was
used to apply the sample, the plate needs to be dried in a vacuum chamber.
 A small amount of an appropriate solvent (elutant) is poured in to a glass beaker or any
other suitable transparent container (separation chamber) to a depth of less than 1
centimeter. A strip of filter paper is put into the chamber, so that its bottom touches the
solvent, and the paper lies on the chamber wall and reaches almost to the top of the
 container. The container is closed with a cover glass or any other lid and is left for a few
minutes to let the solvent vapors ascend the filter paper and saturate the air in the
chamber. (Failure to saturate the chamber will result in poor separation and non-
reproducible results).
 The TLC plate is then placed in the chamber so that the spot(s) of the sample do not
touch the surface of the elutant in the chamber, and the lid is closed. The solvent moves
up the plate by capillary action, meets the sample mixture and carries it up the plate
(elutes the sample). When the solvent front reaches no higher than the top of the filter
paper in the chamber, the plate should be removed (continuation of the elution will give a
misleading result) and dried.

APPLICATIONS

Thin layer chromatography can be used to

 monitor the progress of a reaction

 identify compounds present in a given mixture
 Determine the purity of a substance.
 Specific examples of these applications include: analyzing ceramides and fatty acids,
detection of pesticides or insecticides in food and water, analyzing the dye composition
of fibers in forensics, assaying the radiochemical purity of radiopharmaceuticals, or
identification of medicinal plants and their constituents

A number of enhancements can be made to the original method to automate the different
steps, to increase the resolution achieved with TLC and to allow more accurate quantization.
This method is referred to as HPTLC, or "high performance TLC".

PAPER CHROMATOGRAPHY (PC)

PRINCIPLE


Paper chromatography is an analytical technique for separating and identifying mixtures

that can be colored, especially pigments. This can also be used in secondary or primary colors in
ink experiments. This method has been largely replaced by thin layer chromatography. It is still a
powerful teaching tool. Double-way paper chromatography, also called two-dimensional
chromatography, involves using two solvents and rotating the paper 90° in between. This is
useful for separating complex mixtures of similar compounds, for example, amino acids.

METHOD

Paper chromatography is a technique that involves placing a small dot or line of sample
solution onto a strip of chromatography paper. The paper is placed in a jar containing a shallow
layer of solvent and sealed. As the solvent rises through the paper, it meets the sample mixture,
which starts to travel up the paper with the solvent. This paper is made of cellulose, a polar
substance. The compounds within the mixture travel farther if they are non-polar. More polar
substances bond with the cellulose paper more quickly, and therefore do not travel as far.

APPLICATIONS

 Paper chromatography is for testing the purity of compounds and identifying the
substances.
 Paper chromatography is a useful technique because it is relatively quick and requires
small quantities of material.
 Components of the sample will separate readily according to how strongly they absorb on
the stationary phase versus how readily they dissolve in the mobile phase.

3. Narrate HPLC with neat diagram.

HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC)

PRINCIPLE

High-performance liquid chromatography (sometimes referred to as high-pressure liquid

chromatography), HPLC, is a chromatographic technique used to separate a mixture of
compounds in analytical chemistry and biochemistry with the purpose of identifying, quantifying
and purifying the individual components of the mixture. HPLC is also considered an
instrumentation technique of analytical chemistry.[ instead of a gravimetric technique]

HPLC relies on the pressure of mechanical pumps on a liquid solvent to load a sample
mixture onto a separation column, in which the separation occurs. A HPLC separation column is
filled with solid particles (e.g. silica, polymers, or sorbents), and the sample mixture is separated
into compounds as it interacts with the column particles. HPLC separation is influenced by the
liquid solvent’s condition (e.g. pressure, temperature), chemical interactions between the sample
mixture and the liquid solvent (e.g. hydrophobicity, protonation, etc…), and chemical
interactions between the sample mixture and the solid particles packed inside of the separation
column (e.g. Ligand affinity, ion exchange, etc...).

METHOD

The schematic of an HPLC instrument typically includes a sampler by which the sample
mixture is injected into the HPLC, one or more mechanical pumps for pushing liquid through a
tubing system, a separation column, a digital analyte detector (e.g. a UV/Vis, or a photodiode
array (PDA)) for qualitative or quantitative analysis of the separation, and a digital
microprocessor for controlling the HPLC components (and user software). Many different types
of columns are available, varying in size, and in the type of solid packed particle types available.
Some models of mechanical pumps in a HPLC instrument can also mix multiple liquids together,
and the recipe or gradient of those liquids can modify the chemical interactions that occur in
HPLC’s column, and thereby modify the chemical separation of the mixture.

APPLICATIONS

 HPLC has many uses including medical

Ex detecting vitamin D concentrations in blood serum
 Legal
Ex detecting performance enhancement drugs in urine
 research (e.g. purifying substances from a complex biological sample, or separating
similar synthetic chemicals from each other)a
 Manufacturing (e.g. pharmaceutical quality control).
 Due to the higher pressure separation conditions of HPLC, HPLC columns have
relatively small internal diameter (e.g. 4.6 mm), are short (e.g. 25 mm), and packed more
densely with smaller particles, which helps achieve finer separations of a sample mixture
than ordinary liquid chromatography can.

4. Describe Gas chromatography with neat diagram.

Gas chromatography is used to separate organic compounds that are volatile. A gas
chromatograph consists of a flowing mobile phase, an injection port, a separation column
containing the stationary phase, a detector, and a data recording system.

Mobile phases are generally inert gases such as helium, argon, or nitrogen.

The stationary phase is in the column, if the stationary phase is solid, adsorption takes place. It is
called gas solid chromatography, if the stationary phase is liquid, partition takes place. It is called
gas liquid chromatography.
There are three components in gas chromatography

i) Injection port
ii) Column
iii) Detector

Injection port:

The injection port consists of a rubber septum through which a syringe needle is inserted to inject
the sample.

The injection port is maintained at a higher temperature than the boiling point of the least volatile
component in the sample mixture.

Column:

Since the partitioning behavior is dependent on temperature, the separation column is usually
contained in a thermostat-controlled oven.

Separating components with a wide range of boiling points is accomplished by starting at a low
oven temperature and increasing the temperature over time to elute the high-boiling point
components.

Most columns contain a liquid stationary phase on a solid support. Separation of low-molecular
weight gases is accomplished with solid adsorbents

Gas chromatography columns are of two designs: packed or capillary. Packed columns are
typically a glass or stainless steel coil (typically 1-5 m total length and 5 mm inner diameter) that
is filled with the stationary phase, or a packing coated with the stationary phase. Capillary
columns are a thin fused-silica (purified silicate glass) capillary (typically 10-100 m in length
and 250 µm inner diameter) that has the stationary phase coated on the inner surface. Capillary
columns provide much higher separation efficiency than packed columns but are more easily
overloaded by too much sample.

The most common stationary phases in gas-chromatography columns are polysiloxanes, which
contain various substituent groups to change the polarity of the phase. The nonpolar end of the
spectrum is polydimethyl siloxane, which can be made more polar by increasing the percentage
of phenyl groups on the polymer. For very polar analytes, polyethylene glycol (a.k.a. carbowax)
is commonly used as the stationary phase. After the polymer coats the column wall or packing
material, it is often cross-linked to increase the thermal stability of the stationary phase and
prevent it from gradually bleeding out of the column.

Small gaseous species can be separated by gas-solid chromatography. Gas-solid chromatography

uses packed columns containing high-surface-area inorganic or polymer packing. The gaseous
species are separated by their size, and retention due to adsorption on the packing material.
Detectors:

After the components of a mixture are separated using gas chromatography , they must be
detected as they exit the GC column . The thermal-conductivity (TCD) and flame-ionization
(FID) detectors are the two most common detectors on commercial gas chromatographs. The
requirements of a GC detector depend on the separation application. For example, one analysis
might require a detector that is selective for chlorine-containing molecules; another analysis
might require a detector that is non-destructive so that the analyte can be recovered for further
spectroscopic analysis. Specific GC detectors are Atomic-emission detector (AED),
Chemiluminescence detector and Electron-capture detector (ECD). The ECD is as sensitive as
the FID but has a limited dynamic range and finds its greatest application in analysis organic
molecules that contain electronegative functional groups, such as halogens, phosphorous, and
nitro groups. Flame-ionization detector (FID) The FID is extremely sensitive with a large
dynamic range; its only disadvantage is that it destroys the sample. Flame-photometric detector
(FPD) Mass spectrometer (MS) Mass spectrometers provide structural information to identify the
analyte in a chromatographic peak. Nitrogen-phosphorus detector (NPD) is a detector similar in
design to an FID but with selectivity for compounds containing nitrogen and phosphorus. Photo
ionization detector (PID) Thermal conductivity detector (TCD) The TCD is not as sensitive as
other detectors but it is non-specific and non-destructive.

5. Derive Beer- Lambert’s law and write its limitations.

Lambert’s Law states that, “When a beam of monochromatic radiation is passed through
a homogeneous absorbing medium the rate of decrease of intensity of the radiation dI
with thickness of absorbing medium dx is proportional to the intensity of the incident
radiation I as well as the concentration of the solution C”.
Intensity of incident radiation = I
𝑑𝐼
Decrease in intensity = - [ 𝑑𝑥 ]

Concentration of solution =C
Thickness of the absorbing medium = x
According to Beer- Lamberts Law,
𝑑𝐼
- [ 𝑑𝑥 ] α C I
𝑑𝐼
- [ 𝑑𝑥 ] = K C I
𝑑𝐼
- [ 𝐼 ] = K C dx

Where K is absorption co-efficient,

When I = Io at x = 0 & I = I at x= x
Integrating the above equation, we get
𝐼 𝑋
∫𝐼0 𝑑𝐼/𝐼 = - K C ∫0 𝑑𝑋

ln 𝐼 − ln I0 = - K C [𝑥 − 0]

=-KCx

𝐼
2.303log 𝐼0 = - K C x
𝐼 𝐾
log 𝐼0= -2.303 𝐶𝑥
𝐼
log 𝐼0 =ϵ C x
𝐾
Where ϵ=2.303 = molar extinction coefficient.

𝐼
log 𝐼0 = 𝐴 = ϵ C x

Where A= Absorbance

A= ϵ C x
The above equation is known as Beer-Lambert’s law.
Thus, the absorbance is directly proportional to concentration (C) and thickness (x) of the
solution.
Application of beer-lamberts law:
Determination of unknown concentration
First, the absorbance (As) of standard solution with known concentration (Cs) is measured.
According to Beer lamberts law,
As= ϵ Cs x
As
= ϵ x-------------- (1)
Cs

Then the absorbance (Au) of solution with unknown concentration (Cs) is measured.
According to Beer lamberts law,
 Au= ϵ Cu x
Au
= ϵ x------------- (2)
Cu

From equation 1 and 2

As Au
= Cu
Cs
As
Cu= Cs×Cs--------------- (3)

Au and As are measured experimentally and Cs is known. Cu can be calculated from the
equation (3)
Limitations:
 Beer – Lambert’s law is not obeyed if the radiation used is not monochromatic.
 It is applicable only for dilute solutions.
 The temperature of the system should not be allowed to vary a large extent.
 Deviation may occur , if the solution contains impurities.


6. Draw the block diagram of UV spectrophotometer and write its principle.

UV-VISIBLE SPECTROSCOPY
Wavelength of UV region is 200 to 400nm
Wavelength of Visible region is 400 to 800nm
Principles
When a beam of white light is allowed to pass through a glass cell or cuvette filled with a
sample liquid, the emergent electromagnetic radiation that is coming out of the sample liquid
with specific concentration has less power than incident light. The loss of power of the emerging
radiation is due to the absorption of radiant energy by the liquid sample. The absorption of
radiant energy is proportional to the concentration of the sample.
The absorption of radiation in the UV and Visible regions of the spectrum results in the
transition of valence electrons from the lower electronic energy level to higher energy level in a
molecule or ion.
E1 – Eo = hν
Eo – Energy of the electrons in the ground state
E1- Energy of the electrons in the first excited state
 h-Planck’s constant
ν-frequency of the radiation
hν or absorption energy is equal to the amount of energy required for transition from
ground state to excited state of the electrons.

INSTRUMENTATION
Two different types of instruments are available for measuring absorption in the uv-
visible regions. They are photometers and spectrophotometer.
Photometer
The term photometer refers to any inexpensive instrument that measure the intensity of
radiation using filters to eliminate unwanted wavelength of the radiation and either a photo cell
or photo tube to measure the radiation intensity.
Spectrophotometer
This instrument uses a monochromator that scans the entire UV and Visible regions. The
photo multiplier is used as a detector to measure the intensity of radiation.

Block diagram:

SOURCE MONOCHROMATOR SAMPLE

RECORDER DETECTOR

Components:
1. Radiation source
 Tungsten filament lamp - visible region (400 to 740nm)
 Deuterium lamp - UV region.(200 - 400nm)
 Hydrogen discharge lamp

2. Monochromator
It allows the light of required wavelength to pass through and absorb the light of
unwanted wavelength. Normally quartz, prisms or gratings are used as Monochromators.
3. Sample holder:
This is used to hold the sample solution and the reference solution, and to permit efficient
radiation of the sample.
Glass cells – 300 to 2500nm
Corex cells – 210 to 300nm
Silica glass – lower wavelength
4. Detectors:
These are used for measuring the intensity of the radiation at each frequency after passing
through the sample and hence to measure the amount of energy absorbed at each of these
frequencies by the sample. The different types are
 Photo tube
 Photo multiplier cells
 Photo voltaic cell
 Photo diode
5. Recorder:
This consists of either a pen-recorder or a computerized data station, with a VDU for
initial viewing of the spectrum, with the possibilities of manipulation in scale.
APPLICATONS:
1. Quantitative analysis (based on Beer’s law).
2. Photometric titrations.
3. Structure determination.
4. Measurement of dissociation constants of acids and bases.
5. Kinetic studies.
7. How will you estimate metals by flame photometer?

Flame Photometry (Or) Flame Emission Spectroscopy:

Intensity of emitted light is measured, when metal is introduced in to the flame.
 Wave length of color tells what the element is
 Intensity of color tells how much the element is

Principle:

Instrumentation
i) BURNER : Flame excitation unit
ii) MIRROR: Radiation is emitted: to increase amount of radiation concave mirror used.
iii) SLITS: Entrance slit: Permit radiation
Exit slit: Prevent entry of interfering lines.

iv) MONOCHROMATOR/PRISM/GRATING/FILTER:
Allows the light of required wavelength
v) DETECTOR :
 Measure the intensity of radiation and Converts radiation into electric current
vi) AMPLIFIER: Record the current

WORKING
Air + sample solution + Fuel gas mixture burnt in burner

Radiation emitted
passed
Lens, Filter, Detector, Amplifier and Recorder.
Experiment carried out for a serious of std. solutions. Graph plotted between concentration &
intensity of emitted light
Applications of Flame Photometry

1. ESTMATION OF SODIUM BY FLAME PHOTOMETRY

Instrument is switched on.

Air & gas supply regulated

Distilled water is sent.

Warmed for 10 mins

Instrument adjusted for zero degree

Sodium produces yellow emission at 589 nm, the instrument is set

Readings are noted for a series of std NaCl solution.

Graph plotted between concentration & intensity of emitted light, straight line is obtained

Intensit
y of Unknown
emitted Concentration
light
Concentration
mg/lit
QUALITATIVE ANALYSIS QUANTITATIVE ANALYSIS
Element χ - max Colour of flame Elements in group I & II (Alkali &
Alkaline
earth metals.
Ca 422nm Brick red Transition elements such as Cu, Fe,Mn

K 766nm Red
Na 586nm Yellow
Li 670nm Scarlet red

Other Applications :
Medicine, Agriculture, Plant science
Analysis of biological fluids, tissues
Soil analysis
Industrial & natural waters
Petroleum products
Cement,glass,metallurgical products

8. Explain the principle and instrumentation of IR spectroscopy.

INFRARED SPECTROSCOPY
IR spectroscopy is a powerful technique used for chemical identification and also quantitative
analysis.
The IR region lies between about 0.75µm (750 nm) to about 1000 µm.
This can be further divided into two types: 1. Near IR – 0.75 – 2.5 µm, 2. Far IR – beyond 16
µm
PRINCIPLE
The absorption of radiation by a sample requires that
(a) The energy content of radiation should correspond to the energy difference between
the two vibrational states
(b) The change in dipole moment during absorption process.

Types of Vibration
(i) Stretching vibration (ii) Bending vibration.
INSTRUMENTATION:
There are three basic components in an infrared spectrophotometer:
1. A stable source of radiant energy.
2. A monochromators for isolating a desired narrow region of infrared radiation.
3. A detector for measuring the transmitted radiation.

SOURCE SAMPLE MONOCHROMATOR

RECORDER DETECTOR

Infrared spectrophotometers have the sample placed before the monochromators.

RADIATION SOURCES:
IR instruments require a source of radiant energy which emits IR radiation which must be
steady, intense enough for detection and extend over the desired wave length. Various sources of
IR radiations are as follows.
a) Nernst glower
b) Incandescent lamp
c) Mercury arc
d) Tungsten lamp
e) Glober source
f) Nichrome wire

SAMPLE CELLS AND SAMPLING OF SUBSTANCES

Cells:
The most commonly used cells are made from sodium chloride as this material is
transparent to infrared radiation and inert towards the samples.
Sampling techniques:
IR spectroscopy has been used for the characterization of solid, liquid or gas samples.
 i. Solid - Various techniques are used for preparing solid samples such as pressed pellet
technique, solid run in solution, solid films, mull technique etc.
ii. Liquid – samples can be used as a liquid. Sample cells are made of alkali halides.
Aqueous solvents cannot be used as they will dissolve alkali halides. Only organic
solvents like chloroform can be used.
iii. Gas – They are taken in a 10cm long cell. The sample in drawn into an evacuated cell
to the desired pressure.
MONOCHROMATORS:
Various types of monochromators are prism, gratings and filters. Prisms are made of Potassium
bromide, Sodium chloride or Cesium iodide. Filters are made up of Lithium Fluoride and
Diffraction gratings are made up of alkali halides.
Sodium chloride is the most often used prism material for the wavelength range from 2.5 to
15µm (4000-600cm-1).
Focusing is done by very efficient and rugged glass or quartz mirrors which are coated with
gold or aluminium.
DETECTORS:
Detectors are used to measure the intensity of unabsorbed infrared radiation.
 Thermocouples
 Bolometers
 Thermisters
 Golay cell
 Pyro-electric detectors
RECORDER: Recorders are used to record the IR spectrum.
Applications:
1. Quantitative analysis
2. Structural determination
3. Interpreting infrared spectra
4. Identification of a polymer sample
5. Impurities present in a organic compound

9. Discuss the principle and working of Atomic absorption spectroscopy (AAS)

Atomic Absorption Spectroscopy (AAS)
Energy absorbed by the sample is used to find its characteristics. Sometimes absorbed
energy causes light to be released from the sample, which may be measured by a technique such
as fluorescence spectroscopy.
Principle
When the light of the required wavelength is allowed to pass through a flame, having
atoms of the metallic species, part of that light will be absorbed by the ground state gaseous
atoms.
Absorption radiation is directly proportional to the concentration of the atom in the
flame.

INSTRUMENTATION

SOURCE FLAME WAVELENGTH DETECTOR

SELECTOR
ATOMIZER
SIGNAL
PROCESSOR AMPLIFIER
SAMPLE
PROCESSOR

Components
1. Light Source
 Hollow cathode lamp It contains a tungsten anode and a hollow cylindrical cathode
made of the element to be determined. These are sealed in a glass tube filled with an inert
gas (neon or argon). It emits stable intense radiation.
 Electrode less discharge lamps
 Deuterium lamps
2. Atom cell (Atomizer)
The role of the atom cell is to primarily dissolvate a liquid sample and then the solid
particles are vaporized into their free gaseous ground state form.
3. Monochromator
It is used to select a given absorbing line from the spectral lines emitted from the cathode
lamp. The selection of the specific light allows the determination of the selected element in the
presence of others.
4. Detector and Read out Device.
The light selected by the monochromator is directed onto a detector that is typically a
photomultiplier tube, whose function is to convert the light signal into an electrical signal
proportional to the light intensity.
The processing of electrical signal is fulfilled by a signal amplifier. The signal could be
displayed for readout or further fed into a data station for printout by the requested format.
WORKING
 Radiation passes through a flame.
 Metallic compounds are decomposed into the atoms
 Atoms absorb a fraction of radiation from the flame
 Unabsorbed radiations from flame pass through monochromator
 Unabsorbed radiations is led into detector
 Output is amplified & recorded.

Applications:
There are many applications for atomic absorption:
Clinical analysis: Analyzing metals in biological fluids such as blood and urine.
Environmental analysis: Monitoring our environment – e g finding out the levels of various
elements in rivers, seawater, drinking water, air, and petrol.
Pharmaceuticals: In some pharmaceutical manufacturing processes, minute quantities of a
catalyst used in the process (usually a metal) are sometimes present in the final product. By using
AAS the amount of catalyst present can be determined.
Industry: Many raw materials are examined and AAS is widely used to check that the major
elements are present and that toxic impurities are lower than specified – e g in concrete, where
calcium is a major constituent, the lead level should be low because it is toxic.
Limitations:
1. It is limited only to metals and metalloids.
2. Does not provide information on chemical form of the metal.

10. Write briefly the applications of IR and UV-Visible spectroscopy

Application of IR:

1. Quantitative analysis
2. Structural determination
3. Interpreting infrared spectra
4. Identification of a polymer sample
5. Impurities present in a organic compound
Application of UV:

1. Quantitative analysis (based on Beer’s law).

2. Photometric titrations.
3. Structure determination.
4. Measurement of dissociation constants of acids and bases.
5. Kinetic studies.