Merged document 4

CHAPTER - 1. High Polymers and Elastomers
 The compound formed by large number of small molecules (called monomers) linked together are known as POLYMERS
[poly = many].
 Thus the single repeating unit is called as monomer, and the resultant high molecular weight compound is called as polymer.
Classification of polymers
Tacticity
a) Isotactic polymers
b) Atactic polymers
c) Syndiotactic polymers
In isotactic, the head to tail configuration in macromolecule
with respect to functional group is iso, i.e. all the functional groups lie
on the same side of the chain.
In atactic, the head to tail configuration is random i.e. the functional
groups are arranged randomly.
In syndiotactic polymers, the functional groups occupy the alternating
position.
Condensation/Step polymerization.
 [May 2004, Dec.2004, May 2006, Dec.2006, May 2007, Dec. 2007]
The monomers having certain functional group such as -
OH, -COOH,
-N etc. show the tendency to undergo polymerizations by
the elimination of one molecule of a simple by-product such
as , Salt or alcohol etc. Unlike addition/chain
polymerizations, polymer loses simple molecules at every
combination.
Thus,
i. Condensation Polymerization is undergone by the monomers
which possess functional groups.
ii. Generally monomers are like acids, amines, alcohols,
phenols, carbonyl compounds etc.
iii. This type of polymerization occurs stepwise, hence the rate
of polymerization is comparatively low.
eg. Ureaformaldehyde
 In the formation of ureaformaldehyde, hydrogen from group of urea condenses with oxygen to form ureaformaldehyde
with free valency and eliminates water molecule as shown in reaction.
 These terminated groups further condense with formaldehyde to form long chains, thus the urea formaldehyde can be
represented can be represented as,

Plastics
 The name plastic refers to its meaning that these are the polymers which mould themselves into articles by heat and pressure.
Comparison of Plastics
 [Dec.2003, May 2005, Dec.2005, May 2006, May 2008]
Sr.
No.
Thermoplastics or thermosoftening
Plactics
Thermosetting Plastic or
Thermohaidening Plastics
1. These are formed by addition polymerization These are formed by condensation polymerization
only
2. They are long chain linear polymer with negligible
cross links
These have three-dimensional network structure with
number of cross links
3. Structural formula: Structural formula:
4. Monomer used in these is generally bifunctional In this, monomer used is of higher functionality
5. They have low molecule weight They have high molecular weight
6. They are usually soft, weak and less brittle. They are usually hard, strong and more brittle
7. They are usually soluble in some organic solvents. Due to strong bonds and cross links, they are insoluble
in almost all organic solvents
8. They get softened on reheating readily because second
ary force between the individual chain can break by
heat or pressure.
They do no soften on heating because the cross links
and bonds retain their strength on heating and hence.
9. They can be softened, reshaped and thus reused.
(reclaimed from waste) (by reheating to a suitable
temperature)
They retain their shape and structure even on heating.
Hence, they cannot be reshaped and reused. (cannot
be reclaimed)
10. Example : Polyethylene, polystyrene, PVC, PVA Example : Phenolformadehyde, ureaformaldehyde,
Nylon 6:6.
Fabrication of Plastics or Moulding of Plastics
 [Dec.2003, Dec.2007, May 2008]
 The fabrication is the process in which the prepared resins in the form of granules or powder are converted into desired shape
by using various machines or moulds.
 The basic principle involved in this is partially melting (softening) resinous mass by the application of heat.
Compression Moulding
 [Dec.2003, May 2005]
 It is one of the most common method for moulding
thermosetting materials which can withstand high temperature
and pressure.
 This process consist of compressing the molten resinous material
into the desired shape by the use of moulds, heat and pressure.
 A predetermined quantity of resin powder of pallets is usually
preheated to about 120 C before the cavity of the heated mould
is filled with it.
 After charging the mould, the two parts of moulds are carefully
brought together under low pressure. (Refer Fig.)
 It is then compressed by hydraulic pressure.
 Pressures from 2,000 to 10,000 p.s.i are used.
 This pressure and heat allow the resin to melt and flow, thereby filling the cavity between the two parts of the mould.
 The material in the mould is kept for the specified time under a correct temperature and pressure for a proper curve. The
curing is done either by heating (in case of thermosetting) or cooling (in case of thermoplastics).
 After curing, the moulded articles are taken out by opening the mould apart.
 A varity of products ranging from ash trays and elastric switch boxes to radio and television cabinets are manufactured this
way.
Injection Moulding
 It is one of the most widely used processes for converting thermoplastic raw
materials into finish product.
 It is fundamentally simple and capable of producing a very wide range of
industrial and domestic articles.
 In this process a predetermined quantity of the granular or powdered resin is
fed into a heated cylinder from where it is injected at a controlled rate
through a nozzle into the tightly locked mould by means of a screw
arrangement or by position plunger as shown in the fig.

 Pressure upto 1758 kg/cm is used for injections. The mould is kept cold to allow the hot plastic to cure and become rigid.
 When the material has been cured sufficiently, half of the mould is opened to allow the ejections of the finished article without
any deformation.
 The entire cyclic operation may be made automatic.
 This method is most widely used for moulding of thermoplastic because of high speed production, low mould cost, very low
loss of material and low finishing cost.
 However, there are limitations of design of articles to be moulded because of large number of cavities cannot be filled
simultaneously.
Transfer Moulding
 It is the method which uses the principle of injection moulding and is used for thermosetting materials.
 When relatively intricate designs are required in the fabricated
products, especially when metal insets are to be fabricated, transfer
moulding is used.
 Though transfer moulding is the combination of injection and
compression moulding, it differs from both these methods.
 In this moulding, powdered resins are placed in the heated chamber,
maintained at a minimum temperature at which the powered resins
just begins to become plastic.
 This plastic material is then injected through an orifice into the
mould by plunger, working at a high pressure.
 Due to a very high friction developed at the orifice, the temperature
of the material at the time of ejection from the orifice rises to such an
extent that the moulding powder becomes almost liquid, and
consequently it flows quickly into the mould which is heated upto
curing temperature required for setting.
 The moulded article is then ejected mechanically.
Advantages
1. Intricate shapes not attainable by compression moulding can readily be produced.
2. Article produced is free from flow mark.
3. Even thick pieces cure almost completely and uniformly.
4. Finishing cost of fabricated article is almost entirely eliminated.
5. Blistering is almost eliminated, since air and excluded gases are expelled in the plasticizing chamber itself.
6. Mould cost is less, since it involves very low abrasive action.
7. Fine wires and glasses fibers can be inserted into the mould.
Extrusion Moulding
 [Dec.2005]
 It is mainly used for manufacturing moulding articles of
thermoplastic resins.
 For example tubes, rods, strips, insulated electric cable etc.
 In this method dry moulding powder or granular material is
first fed through hopper into the rear of the heated chamber
which has a resolving screw.
 When the screw is rotated the molten material is pushed
forward through the small orifice of the die to form
continuous uniform shaped articles.
 When the article leaves the orifice, it is allowed to passed
through water for solidification of plastic material.
 The control of the temperature of heating chamber and
speed of the extruder screw are the two most important
factors of successful extruder operation.
There are two types of moulding.
1. Vertical extruder moulding.
2. Horizontal extruder moulding as shown in the following fig.
Name Synthesis Properties Uses
[1]Poly
Styrene
(1) Polystyrene is a transparent, light (Sp.
Gravity 1.05 to 1.07 g/ ) and
stable material.
(2) It has excellent moisture resistance.
(3) it can be nitrated by fuming nitric and
sulphonated by conc. , at about
100 C to yield water soluble emulsion.
(4) It is a highly electric insulating material.
(5) It is highly resistance to acids and has a
In moulding of article like
(1) Toys, combs, buttons
(2) Bucket, radio and television
parts
(3) Refrigerator parts, battery
cases
(4) High frequency insulators
(5)Lenses
(6) Indoor-lighting panels etc.

good chemical resistance.
(6) it has a relatively low softening range
(90 to 100 C) and is brittle.
(7) It has an unique property of transmitting
light through curved section.
[2]PMMA (1) It is transparent and colourless plastic.
(2) Easy to mould in desired shapes.
(3) Refractive index is 1.59
(4) At lower temperature (R.T.) it is brittle
and rigid
(5) When heated slowly, acquires rubber
like properties at about 65 C where as so
items at about 130 C.
Use for making
(1) Artificial eyes
(2) Screens for T.V.
(3) Air crafts, light fixtures
(4) Also used in optical
instruments, bone splints,
adhesives, paints etc.
(5) In skylights, decorative
articles etc.
[3] Phenol
Formaldehyde
(1) They are scratch resistant, water
(2) resistant, water resistant and insoluble
solids.
(3) They possess excellent electrical
insulating character.
(1) For making electronic
(2) insulator parts like switches,
plugs, switch boards, heater handles etc.
(3) For making moulded articles
like telephone parts, cabinet
for radio and television etc.
(4) As a binder for grinding wheels.
(5) It is used in paints and
vanishes.
[4] Urea
Formaldehyde
(1) They possess good electrical insulating character.
(2) Resistant to water.
(3) Resistant to heat/flame.
(1) Used as a binder of glass fibers, rock wool etc.
which are used for
filtration and insulation purpose.
(2)Used in bonding plywood.
(3) Used as an electrical insulation.
(4) For decorative articles like
plates, drinking glasses, dishes etc
Urea formaldehyde
 [Dec.2003, Dec.2004, May.2006,
May.2007, May.2008]
Synthesis
 These are also called as amino resins
or amino plants.
 In general amino organic compounds
and formaldehyde combine by
condensation polymerization to give
these resins.
 In this particular types of resins,
organic amine being urea, reacts with
formaldehyde and polymerises to
give resins.
Reaction
Properties and Drawbacks of natural Rubber
 [Dec.2003]
 The natural rubber has following properties, (drawbacks) :
1. Its plasticity is greater than elasticity. It cannot sustain stress. Thus when stretched to a great extent, it undergoes deformation
permanently.
2. It has large water absorption tendency, which makes it weak.
3. It has very low tensile strength (20 kg/cm ).
4. Due to large percentage of unsaturation in its structure, it is easily attacked by various reagents such as , conc. ,
organic solvents, air, oxygen, ozone etc. and as a result gets gradually disintegrated.
5. It possesses high percentage of tackiness (Property of developing stickiness on surface) which makes it difficult to store the
rubber stocks.
6. Durability and abrasion resistance of natural rubber is very low.
 Thus the natural rubber does not have the desirable properties.
 Hence to make its maximum use, it is essential to improve its properties by means of certain catalyst.
 Any catalyst used to improve the drawbacks of natural rubber is known as a vulcanizing agent, and the process by which the
undesirable properties of natural rubber are improved upon is known as vulcanization.
Vulcanisation

 [Dec.2004, May.2006, Dec.2006, May.2007, Dec.2007, May.2008]
 To improve the properties of raw rubber, it is compounded with some chemicals like sulphur. , benzyl chloride etc.
 Most important of all the process of compounding (vulcanizing) is the addition of sulphur.
 The process consist of heating the crude rubber with sulphur to a high temperature.
 The sulphur combines chemically at the double bond in the rubber molecule. Vulcanization brings about stiffening of the
rubber by a sort of cross-linking and consequently preventing inter molecular movement or sliding of rubber springs.
 The extent of stiffness or loss of elasticity of vulcanized rubber depends upon the amount of sulpher added.
 For example, a tyre rubber may contain 3 to 5% sulphur, but a battery case rubber may contain as much as 30% sulphur.
 The changes in properties that take place due to vulcanization is shown as below :
Undesirable properties Improvement
Tacky Non-tacky
Weak Vulcanization Strong
Plastic Elastic
Soluble Insoluble
Advantages of using vulcanization
1) It has good tensile strength and extensibility when tensile force is applied.
2) It possesses low water absorption tendency.
3) It has much higher resistance to wear and tear.
4) It is a better electrical insulator.
Co-polymerisation
 [May.2005, Dec.2007]
 Copolymerization is nothing but specific type of addition polymerization.
 In this the monomers of more than one type are involved.
 Copolymerization has unique importance in the industry.
 This is because products formed by copolymerization shown the specific properties of the monomers.
 Sometimes such special properties are further enhanced or sometimes unique properties in the product as a result of the
reaction between two different types of monomers.
 Thus copolymerization gives rise to variety of the products.
 Thus several useful and commercially important polymers are formed by copolymerization.
e.g. Styrene butadiene rubber (SBR – GR – S)
Acrylonitrile rubber NBR or GR – A
 Example : Ethylene copolymerized with propylene and also propylene copolymerised with butadiene gives rise to plastic
resistance to oxygen, and heat.
 Properties of the copolymers depends on the relative amount of the two monomers constituting a polymers and also on the
type of monomer.
Polymer Crystallinity
 [Dec.2007]
It is a property a polymer exhibits in varying extent, which is based on the pattern of arrangement of molecules of polymer.
A polymer is said to be „crystalline‟ if all molecules are arranged in orderly compact manner with symmetrical orientation,
with higher force of attraction between two chains.
Crystalline polymers generally,
1) Posses high density.
2) Strong, hard but brittle
3) Have sharp M.P.
This property can be calculated by density measurement of sample and of other known highly crystalline to highly
amorphous polymer. Then,
% crystallinity =
density of sample d – ensity of highly crystalline dc polymer
dc – da
Visco-elasticity of polymers
 [Dec.2007]
Physical state of a polymer is governed by chain length and molecular weight.
Based on molecular weight, polymers are either elastic solids or viscous
liquids.
These physical states are temperatures servitive.
If cooled slowly, polymer becomes hard and brittle, and vice-versa.

 The time taken for cooling/heating also plays equally important role.
 Thus with variation in temperature and time duration between the range of temperature, a polymeric material exhibits different
range of viscocities. This behaniour of a polymer is known as “viscoelasticity”
Melting and Glass Transition
 [Dec.2007, May 2008]
 The behavior of polymer with respect to its flow properties
is temperature sersitive.
 When a polymer is cooled slowly, it becomes more and
more viscous, finally becomes hard solid and brittle. At this
stage polymer behaves like glass, and breaks if stressed.
 Glass Transition temperature is defined as, “the lowest temperature beyond which the polymer becomes hard, glass-like and
brittle and the high temperature above which it becomes flexible, soft and elastic like rubber.”
 It is denoted as and respectively.
 Thus a polymer changes states as follows:
 In viscoelastic state, polymer molecule has total flexibility, which diminishes beyond , and brittleness is developed.
 Above , polymer is in molten state, where it does not exhibits and shape.
 Thus between and , polymer can sustain stress, because all along the chains, the stress gets distributed almost equally.
 As compared to is an important property for polymer because the value(or range of it)of helps to anticipate flow
properties/softening temperatures of polymers. By the different samples can be compared and selection of polymer for
desired moulding can be done more efficiently.
 depends upon molecular structure presence of side chain, polar group and also on chain length iucluding frequency of
repeating groups along chain. The geometry of molecule also influences .
 Example : increases if aromatic ring is present or high M.W, stronger intermolecular forces of attraction, coiling of
molecule etc.
Supra molecular chemistry and molecular electronics
 [May.2008]
 Supra molecular chemistry is a relatively new field of chemistry which focuses quite literally on going “beyond” molecular
chemistry.
 It can be describe as the study of systems which contain more than one molecule, and it aims to understand the structure,
function and properties of these assemblies.
 Examples of super molecular systems include biological membranes , polynuclear metal complexes, liquid crystals, and
molecule-based crystals.
 A cell (very complex) supermolecular system biopolymers such as nucleic acids, and proteins.
 A supermolecular assembly is a multi component system of atoms, ions and/or molecular, which are held together by non-
covalent interactions such as hydrogen bonds, van der waals forces, pi-pi interactions, and/or electrostatic effects.
 The latter mode of bonding is particularly important for assemblies involving metal ions.
 These various bonding interactions are far weaker than covalent bonding (which are the kind of bonds which hold molecules
together) therefore supermolecular assemblies are usually far less stable than molecular compounds (for example, they can be
more susceptible to breaking apart at high temperatures or if they are mixed with acid).
Formation od Supermolecular Assemblies
 [May.2008]
 The most common method is to use self-assembly techniques, in which the different components are mixed under given set of
conditions (solvent, temperature, pH etc.) and then they are allowed to form assembly.
 Such self-assembly process form a single product which is result of the countless possible combinations of the starting
materials.
 Such supermolecule (product) is formed because it is the most thermodynamically stable arrangement of the constituent
entities.
 If in case the combinations take some wrong path which may be thermodynamically unfavoured, the molecule breaks
immediately.
 This type of „reversibillity‟ id one of the unique features of supermolecular synthesis and this is the major difference between
the molecular synthesis and the conventional molecular synthesis involving covalent bonds.
 In molecular synthesis, a reaction which goes down the „wrong pathway‟ often ends up at a dead end and the material which is
formed must in the end be separated from the desired product.
 One of the major goal of supermolecular chemists is the synthesis of supermolecular assemblies which have new functions
that cannot appear from a single molecular or ion.
 These functions are based on novel magnetic properties, light responsiveness, catalytic activity, fluorescence, redox properties,
etc., of super molecular systems.
 These useful properties may lead to the application of these assemblies as and thse is the list of random examples high-tech
sensors for pollutants in air or water, compact information storage device for next-generation computers, as high-performance
catalysts in industrial processes, or as contrast agents for CAT scans.
 Supermolecular chemistry is intimately related to nanotechnology, and many promising nanotech devices are based on the
principles of supermolecular chemistry.

Subdivision of supermolecular chemistry
 Supermolecular
 Host-guest chemistry
 Helicates
 Catenenes
 Rotaxanes
 Knotanes
 Supra molecular Assemblies
 Micelles
 Membranes
 Vesicles
 Liquid crystals
ADDITIONAL
 Viscoelasticity
Physical state of a polymer is governed by chain length and molecular weight. Based on molecular weight, polymers
are either elastic solids or viscous liquids/flowy liquids.
These physical states are temperatures servitive. If cooled slowly, polymer becomes hard and brittle, and vice-versa.
The time taken for cooling/heating also plays equally important role.
Thus with variation in temperature and time duration between the range of temperature, a polymeric material exhibits
different range of viscocities. This behavior of polymer is known as “viscoelsticity”
 Short note
Conducting Polymers.
Ans. :
Polymers, generally with high crystallinity, are more commonly, developed conductivity more easily.
e.g. Cis-polyacetylene or poly para phenylene
These are following types of conducting polymers :
1. Intrinscially conducting polymers (ICP)
2. Doped conducting polymers (DCP)
3. Extrinsicially conducting polymers (ECP)
4. Co-ordination conducting polymers (CCP) (Inorganic polymers)
Characteristics of each type are discussed in brief.
ICP
These possess conjugated electrons backbone. When such polymer faces electric field, these electrons get excited,
and hence move through polymer material. The orbitals of conjugated electrons get overlapped on the backbone and hence
valence bands and conduction bands are developed which get distributed over entire surface of polymer. Appropriate
proportion of conjugated electrons makes polymer to conduct electricity very efficiently.
e.g. Polyacetylences
Polyquinoline
Poly-p-phenylene
Poly-m-phenylene sulphides etc.
Aromatic : Polyaniline, Polyanthrylene
Aromatic hetrocyclic : Polypyrrole, polythiophene, polybutadienylene.
DCP
These are prepared by exposure of the polymer to a charged transfer agent either in gas phase or in liquid phase (i.e.
solution). As compared to plain ICP, these have low I.P. but high E.A/ Hence these can be easily oxidized or reduced.
ICP can be made more conductive by creating + ve ot – ve charge on its backbone by oxidation or reduction.
ECP
These are the conducting polymers which possess conductivity due to externally added ingredient in them.
There are two types of ECPs,
1. Conductive element filled polymer
In this type, resin or polymer is filled up with conducting element.
e.g. carbon black, metallic fibers, metal oxides etc.
The polymer holds the metallic element, thus acting as a binder. Their conductivity is reasonable high.
Properties
1) Cost is low.
2) They are light in weight.
3) Strong.
4) Can be easily moulded.
2. Blended conducting polymer
These are nothing but blend of normal polymer with conducting polymer. The blending is either only physical change or in
certain cases chemical change. They possess good mechanical properties.
Co-ordination Conducting Polymers : (Inorganic Polymers)

These are inorganic in nature, in which a complex involved in transfer of charge is combined with polymer, and a metal
atom is combined with polydentete ligands. They have very low degree of polymerization ( 18). They are corrosion resistant.
Applications of Conducting Polymers
1) In rechargeable light height batteries.
2) Optically display devices.
3) In wiring in aircrafts and aerospace components.
4) In tele-communication systems.
5) In electromagnetic screening material.
6) Solar cells, photovoltaic devices, transistors, diodes, molecular wires and switches etc.
Fabrication in case of
Thermosething Plastic Thermo-softening plastic
 Hot plastic is ultimately solidified Moulded plastic material is
through further polymerization further cooled or chilled for
called „curing‟/setting stage while solidification of
It is still in mould.
 Injection moulding, extrusion, Compression moulding, transfer
blow moulding, vacumm, forming moulding and laminating
techniques are usually used techniques are generally
employed.

CHAPTER-2 WATER AND ITS TREATMENT
Hardness of water
 [Dec.2003, May.2006, Dec.2007]
 Hardness in water is that characteristic, which prevents the lathering of soap.
 Hardness was originally defined as, “the soap consuming capacity of a water sample.”
 Soaps generally consist of sodium salts of long chain fatty acids such as oleic acid, palmitic acid and stearic acid.
 The soap consuming capacity of water is reduced due to the presence of certain salts of calcium, magnesium and other heavy
metal dissolved in it.
 When the ions of these salts react with the sodium salts of long-chain fatty acids present in the soap, lather is not produced but it
forms insoluble white scums or precipitates of calcium and magnesium soaps which do not posses any detergent value.
Or
Or
 Other metal ions like and also react with soap in the same fashion, thus contributing to hardness.
 Further acids, such as carbonic acid can also cause free fatty acid to separate from soap solution and thus contribute to hardness.
 However, in practice, the hardness of a water sample is usually taken as a measure of its and content. Thus we can
defined hard and soft water as follows :
Hard water :
Water which does not produce lather with soap solution readily but forms a white curd is called hard water.
Soft water :
Water which lathers easily on mixing with soap solution is called soft water. Such type of water consequently does not
contain dissolved calcium and magnesium salts in it.
Determination of Hardness by EDTA Method
 [May.2000, Dec.2006]
 EDTA is abbreviation of Ethylene diamine tetra acetic acid.
 This compound dissolves in water with great difficulty and in
a very very small quantity.
 On the contrary its di-sodium salt dissolves in water quickly
and completely. Hence for common experimental purpose, in
place of EDTA, its di-sodium derivative is used.
 EDTA is a hexadentate ligand. It binds the metal ions in water
i.e. or to give highly stable chelate complex.
(These metal ions are bounded via oxygen or nitrogen from
EDTA molecule).
 Therefore, this method is called as complex metric titration.
 The formation and structure of complex is as shown below :
Sodium stearate
(Sodium / Souble soap)
Calcium stearate
(Calcium / insoluble soap)
(ppt or curd)
Magnesium stearate
(Magnesium / insoluble soap)
(ppt or curd)

Principle of EDTA method
 [May.2000, Dec.2005, Dec.2006]
 Ethylene diamine tetra acetic acid (EDTA) forms complexes with and , as well as with many other metal
cations, in aqueous solution.
 These complexes have the general formula as shown above.
 Thus, in a hard water sample, the total hardness can be determined by titrating and present in an aliquot of
the sample with Na EDTA solution, using buffer solution of pH 10 and Eriochrome Black T as the
metal indicator.
 At pH 10, EBT indicator form wine red coloured unstable complex with ions in hard water.
 This complex is broken by EDTA solution during titration, giving stable complex with ions; and releasing EBT
indicator solution which is blue in colour. Hence the colour changes is from wine red to blue (EBT’S own colour).
Reaction
Thus nothing the colour change, the point of equivalence can be trapped and hardness of water can be determine by using this method.
Procedure for EDTA Titration
 [May.2000, Dec.2005]
The steps involved in the determination of hardness of water are summarised here.
Step 1 : Preparation of reagents
Step 2 : Titration
Step 1 : Preparation of reagents
The various solutions required can be made as follows :
(a) Standard hard water
One gram of pure, dry is dissolved in the minimum quantity of dilute HCl. This solution is evaporated to
dryness on a water bath. The residue left is dissolved in distilled water and the solution is diluted to 1 L. The
hardness of this solution would be 1 mg of equivalent per ml.
(b) EDTA solution
3.7 grams of pure EDTA crystals are mixed with 0.1 gram of and dissolved in distilled water and the solution
is made to 1 litre.
(c) Indicator
0.5 gram of EBT is dissolved in 100ml of alcohol.
(d) Buffer solution of pH 10
67.5 grams of are added to 570 ml of concentrated ammonia solution. The mixture is then diluted to 1 litre
with distilled water.
Step 2 : Titration
The following steps are followed to estimate hardness of water sample :
(a) Standardization of EDTA solution

50ml of standard hard water is taken in a conical flask. 10-15ml of buffer solution of pH 10, 4-5 drops of EBT
indicator are added and the solution is titrated against EDTA solution till colour changes from wine red to deep blue.
(Volume of EDTA solution = ml).
(b) Estimation of total, hardness
50ml of hard water sample is titrated as above against EDTA solution (volume of EDTA = ml).
(c) Estimation of permanent hardness
50ml of hard water sample is boiled for about 15-20 minutes, filtered, diluted with distilled water to make 50ml and
titrated as above against EDTA solution. (Volume of EDTA = ml).
Using the data of and ; total and permanent hardness is calculated. The difference of these two values
gives temporary hardness of water.
Advantages of EDTA method
1. Highly accurate.
2. Highly convenient.
3. Highly rapid.
Sludge and Scale Formation
 [Dec.2003, Dec.2004]
 Due to continuous evaporation of water in boilers,
the concentration of dissolved salts in hard water increases progressively and finally when ionic product exceeds the
solubility product, these salts are precipitated on the inner walls of the boiler.
 If the precipitates are losses, slimy, and floating, they are known as sludges.
 If the precipitated matter forms a hard adhering coating inside the boiler surface, they are called as scales.
(a) Sludge
Formation of sludge
 Sludge is a soft, loose and slimy precipitate formed in the boiler. Sludges can be easily removed with a wire brush.
 Sludges are formed in comparatively colder areas of boilers and are collected in areas where flow rate is slow or at
bends in the pipes.
Causes of sludge formation
 Sludges are formed by substances which have greater solubility in hot water then in cold water e.g.
etc.
 Sludges may lead to choking of pipes.
Disadvantages of sludge formation
1. Sludge are poor conductor of heat
2. If sludges are formed along with scales, then former gets entrapped in latter and both get deposited as scales.
3. Excessive sludges if formed in boilers, choke up pipe connection, plug opening, gauge-glass connection and disturb
working of boilers.
Prevention
Sludge formation can be prevented by,
1. Using soft water in boilers
2. Frequent blow down operation i.e. drawing off a portion of the concentrated water (containing large amount of
dissolved salts) and replacing it with fresh water.
(b) Scales
Formation of scales
 Scales are hard deposits which stick very firmly to the inner surface of the boiler.
 As the scales are hard and adherent, it is difficult to remove them even with the help of hammer and chisel.
 They are the main causes of boiler troubles.
Causes of scale formation
1. Decomposition of Ca
2. Deposition of
3. Hydrolysis of magnesium salts
4. Presence of silica

(1) Decomposition of
 The formed is soft.
 In low pressure boilers, it is the main cause of scale formation, however, in high pressure boilers, reacts to give
as sludge and
(2) Deposition of
 This is the main cause of scale formation in high pressure boilers. It is quite adherent and difficult to remove.
 When hard water containing is heated in boilers, , gets precipitated as hard scale on the heated portion of
boilers and forms scale.
(3) Hydrolysis of magnesium salts
Magnesium salts form a soft type of scale at high temperature in boilers.
(4) Presence of silica ( )
 Silica reacts with calcium and magnesium metals to form and/or ,
 These deposits are very difficult to remove.
Disadvantages of scale formation
1. Wastage of fuel
 Scales have low thermal conductivity, so they act as particle obstruction, therefore the rate of heat transfer from wall
of boiler to inside water is decreased greatly.
 In order to get a steady supply of heat to water, over heating is done and this increases fuel consumption depending
on the thickness and nature of scale formed.
 For example, if the thickness of scale is 0.325mm, wastage of fuel is 10% but if thickness is 12mm, wastage of fuel
is 150%.
2. Decrease in efficiency
 Scales may be deposited in the valve and condensers of boiler and can choke them partially.
 This results in decrease in efficiency of boilers.
3. Lowering of boiler safety
 Due to scale formation of the heat provided to boilers is not transmitted perfectly to water, as scales are bad
conductors of heat.
 Therefore, the overheating of the boiler tubes make the boiler material softer and weaker.
 This causes distortion of boiler tubes and makes the boiler unsafe to bear the pressure of the steam, especially in high
pressure boilers.
4. Danger of explosion
 Danger of explosion mounts because the boiler is provided with higher amount of heat, but due to scales the same
amount of heat is not transmitted to water inside.
 Moreover, metal parts of boiler as well as layer of scales undergo expansion, but the extent of expansion is varied.
 Later, a stage comes when thick scales crack due to uneven expansion and hot water comes in contact with boiler
wall. This results in sudden production of large amount of steam because due to overheating, the boiler wall is at a
very high temperature.
 This leads to a sudden increase in pressure which may cause explosion of boiler.
Removal of scale
The scales can be removed from time to time by following methods :
1. If scales are loosely adhering, then they can be removed by scraping with a piece of wood or wire brush.
2. If scales are brittle, then by giving thermal shocks (i.e. heating the boiler and then suddenly cooling with cold water)
they can be removed.

3. If scales are hard and adherent, then they can be removed by using some chemicals to dissolve them. e.g.
scales can be dissolved by using 5 to 10% HCl.
4. If scales are loosely adherent, they can be removed by frequent blow down operations.
Prevention of scale formation
For prevention of scale formation two types of treatments are given which are internal treatment and
external treatment.
internal Treatment
 [Dec.2003, May.2004, Dec.2004, May.2005, Dec.2005, May.2006, Dec.2006, May.2007]
“The treatment is accomplished by adding chemicals to boiler water.”
(a) To precipitate the scale forming impurities in the form of sludges which can be removed by blow-down operation.
(b) To convert them into compounds which will stay in dissolved form in water and hence do not cause any harm.
Internal treatment is corrective treatment for removal of certain defects left in external treatment.
Important internal treatment methods
(a) Colloidal conditioning
 In low pressure boilers, scale formation can be avoided by adding organic substances like kerosene, tannin, agar-agar
etc.
 These substance get coated over the scale forming precipitates, thereby yielding non-sticky and loose deposits similar
to sludge which can be removed by blow down operation.
(b) Phosphate conditioning
 In high pressure boilers, scale formation can be avoided by adding sodium phosphate,
 The soft sludge of and (Which is non-adherent and easily removable) can be removed by blow
down operation.
The main phosphates employed are :
1. [Sodium dihydrogen phosphate (acidic)]. When alkalinity of boiler water is too high and is required to be
reduced to optimum value of pH 9.5 to 10.5, salt is added because it is acidic in nature.
2. [Disodium hydrogen phosphate (weakly alkaline)]. It is used’ when alkalinity of boiler water is adequate.
3. [Trisodium phosphate (alkaline)]. It is used when alkalinity of boiler water is low.
(c) Carbonate conditioning
 In low pressure boilers, scale formation can be avoided by addition of (Sodium carbonate) to boiler.
 formed can be removed by blow down operation.
(d) Treatment with sodium aluminate
 When boiler water is treated with in solution, it gets hydrolysed to yield and
reacts with magnesium salts to form sludge.
 Precipitates of and produced inside the boiler entraps finely suspended and colloidal impurities
including oil drops and silica. The loose precipitates can be removed by blow down operation.
(e) Calgon conditioning
 Sodium hexametaphosphate is added to boiler water. It prevents the scale formation by forming
soluble complex compound. e.g.
(f) Electrical conditioning
 This is achieved by using sealed glass bulbs containing mercury connected to a battery which are set floating in the
boiler.
 When water boils, due to high temperature mercury bulbs emit electrical discharges which prevent the precipitates to
stick to the sides of boiler and this prevent scales formation.
(g) Radioactive conditioning

 Small tablets which contain radioactive salts are placed inside the boiler water at few points.
 As water boils these tablets emit energy radiation and thus prevent scale formation.
Caustic Embrittlement
 [May.2004, May.2006, Dec.2006]
 “Caustic embrittlement is a type of boiler corrosion which makes boiler material brittle.”
This is caused by using alkaline water in the boiler, most commonly in high pressure boiler.
 During lime soda process, free is usually present in small proportion in the softened water.
 in high pressure boilers decomposes to give sodium hydroxide and carbon dioxide.
(This makes boiler water caustic)
 The water containing flows into the minute hair-cracks, in the inner wall of boiler, by capillary action. Here,
water evaporates and the concentration of increases progressively.
 This caustic soda attacks the surrounding areas, thereby dissolving iron of boiler wall as sodium-ferroate. This causes
embrittlement of boiler wall at a stressed part like bends, joints, etc.
 It can be explained by considering the following concentration cell.
 Due to such cell formation, anodic parts get corroded. Caustic embrittlement can be avoided,
1. By using sodium phosphate as softening reagent instead of sodium carbonate
2. By adding tannin or lignin to boiler water, since they block the hair cracks, thereby preventing infiltration of caustic
soda solution into cracks.
3. By adding solution to boiler water which also brocks the cracks.
4. By carefully adjusting the pH of feed water between 8 and 9.
Boiler Corrosion
 [Dec.2001, May.2004,May.2007]
 Boiler corrosion can be defined as, “loss of boiler material or deterioration of its useful properties due to chemical or
electrochemical interaction with its environment.”
 Boiler corrosion occurs due to following reason :
(a) Dissolved oxygen
 It is the main corrosion causing impurity in water. Water, usually contains about 8 ml of dissolved oxygen per litre at
room temperature.
 Dissolved oxygen in water attacks the boiler material at high temperature as shown by the following reactions if
boiler material is of iron.
Removal of DO
(1) Dissolved oxygen can be removed by adding calculated quantity of scavengers such as,
(a) Dissolved oxygen.
(b) Dissolved carbon dioxide.
(c) Acids from dissolved salts present in water.
(d)

Sodium sulphite or hydrazine sulphide etc. The reactions are,
 With hydrazine, dissolved oxygen forms products such as nitrogen and water.
 Nitrogen is harmless. Therefore, hydrazine is an ideal chemical for removal of dissolved oxygen.
 On the other hand with and , sodium sulphate is formed which in high pressure boilers, decomposes
giving
 enters into steam pipes, and forms (sulphurous acid) in stream condenser.
 Nowadays, Azamine 8001-RD has been employed for degassing water in minimum time.
(2) Dissolved oxygen can also be removed by mechanical de-aeration, i.e. by maintaining high temperature, low
pressure and large exposed surface.
(b) Dissolved carbon dioxide
 gas dissolved in water, forms carbonic acid, which has slow corrosive effect on boiler material like any other
acid.
 is also released inside the boiler if water contains bicarbonates, which get decomposed as,
Removal
Carbon dioxide can be removed
1. By adding calculated quantity of . (Ammonium Hydroxide) so that reacts with it to give Ammonium
carbonate.
2. By mechanical deaeration along with .
(c) Acids from dissolved salts (Hydrolysis of dissolved salts)
 if present in water, on hydrolysis liberates free acid as shown by chemical reactions,
(Free Acid)
 The liberated free acid reacts with iron material of the boiler in a chain like reaction producing acid again as shown
below,
Therefore, even small amount of magnesium salt cause corrosion of iron to a large extent.
Removal
It can be avoided by adding alkali from outside to neutralise the acid formed.
 Ion exchange Process
[May.2003, May.2004, May.2005, May.2007]
 In this process, a reversible exchange of icons occur between the stationery iron-exchange phase and the external
liquid mobile phase.
 “Ion-exchange resins are insoluble, cross-linked, long-chain high molecular weight organic polymers which are
permeable due to their micro porous structure, and the functional groups attached to the chains are involved in the
iron-exchanging properties.”
 Cation exchange resins
(Free acid)
(Free Acid) – To continue corrosion of boiler

 Resins containing acidic functional groups etc. exchange their ions with other cautions, which
come in their contact are known as cation exchange resins. These are represent as or .
 These resins are capable of exchanging rapidly cations like and by hydrogen ions.
 Anion exchange resins
 The resin containing basic functional groups (e.g. etc. as hydrochloride) exchange their anions with other
anions, which come in their contact are called as anion exchange resin
 These resins are capable of exchanging rapidly anions by ions.
 Principle of ion exchange process
 Sulphates, cholorides and bicarbonates are converted into corresponding acids and . In order words,
water collected from cation exchanger is free collected from all cations, but is acidic.
 After this, the acidic hard water is passed through an anion exchange bed which removes all the anions like
etc. present in the water, and equivalent amount of ions are released from it to water.
 and ions released from cation exchange and anion exchange bed respectively, which combine to produce
water molecule, as,
 Thus , the water coming out from anion exchange bed becomes free of cations as well as from anions.
 The resulting ion-free water is deionised water or demineralised water.
 Process of ion-exchange/demineralization.
 The hard water is first pass through cation exchange column and then through anion exchange column (Fig.)
 The soft water thus obtained is free from all the cations and anions.
 When column gets exhausted, it is set to regeneration ; and the process is continued . The water obtained is near to
the distilled water quality
(0 – 2 )
 The exchange bed is washed with deionised water and washing (containing and or ) are passed to
sink or drain.
 The exhausted anion exchanger is regenerated by treating it with a dilute solution.
Regeneration

 The exchanger bed is washed with deionised water and washings
( containing or ) are passed to sink or drain.
 The regenerated ion-exchange resins are used again. If water contains sufficient temporary hardness, it is advisable to
remove such hardness first by treating with lime.
Advantages of ion exchange process
1. The process can be used to soften highly acidic or alkaline water.
2. It produces water of low hardness (upto 2 ), therefore, it is good for high pressure boilers.
Disadvantages of ion exchange process
1. The equipment is costly.
2. If water contains turbidity, then the output of process is reduced. Turbidity should be below 10
Distinguish between the following:
Regeneration

Solved Problems
 What is the carbonate and non-carbonate hardness of a sample of water which has the following
impurities per liter,

Solution :
 Conversion in equivalents
Salt Qty. in ppm Multiplication factor equivalent in ppmType of Hardness
12.5 12.5 Carbonate
8.4 10 Carbonate
22.2 20 Non-carbonate
9.5 10 Non-carbonate
33 - - -
6.8 8.09 8 Carbonate
Carbonate hardness is due to
Non-carbonate hardness is due to and
Ans. : Carbonate hardness = 30.5 ppm
Non-carbonate hardness = 30 ppm
Class Work problem
 What is the carbonate and non-carbonate hardness of as sample of water which has the following impurities per
liter,
 Calculate the carbonate and non-carbonate hardness of a sample of water containing :
 (May 2002)
Type 2 :- Calculate hardness by EDTA method.
 25ml of solution (strength 250 mgs per 200ml) required 35ml EDTA solution. Same EDTA
solution was used to titrate 25mk of unknown hard water which consumed 30ml. of EDTA solution. Calculate the
hardness of water sample.
Solution:-
Strength of solution is given as 250 mgs of per 200ml.
That means 25ml. of
contains mgs
Now, 25ml solution requires 35ml EDTA solution
35ml EDTA
1 ml EDTA solution
Now,
25ml hard water requires 30ml EDTA solution
of
of
1000ml hard water of equivalent hardness
Hardness of water of

or
Ans. : Hardness of water = 1072
 0.2 gm of was dissolved in dil and diluted to 200ml. 50ml of this solution required .
Solution:- Here, 0.2 gm of was dissolved in dil. and diluted to 200ml.
i.e. 200msg. of is 1mg/ml
Now,
50ml of standard hard water  48ml of EDTA
i.e. of  48ml of EDTA
1ml of EDTA  50/48 mg of i.e. 1.04 mg of
Now, 50ml hard water  15ml of EDTA solution
i.e.  15 1.04 mg of i.e 15.6 mg of
ml of
Hard water contains mg of
Now, after boiling and filtering the solution, the temporary hardness is removed. So only the permanent hardness
remains.
50ml of standard hard water (after boiling) 10ml of EDTA
i.e. 10 1.04 mg of i.e 10.4 mg
of
Hard water contains  of
permanent hardness = 208 ppm
Temporary hardness = Total hardness – Permanent hardness
= 312 – 208
=104 mg/l = 104 ppm
Ans. : Total hardness = 312 ppm
Permanent hardness = 208 ppm
Temporary hardness = 104 ppm
 50ml of standard hard water containing 1 mg of pure per ml consumes 20 ml of EDTA, 50 ml of water
sample consumes 25 ml of EDTA using Eriochrome Black-T indicator, 50 ml of water sample after boiling and
filtering require 18ml of EDTA using same indicator. Calculate temporary and permanent hardness.
PROBLEMS BASED ON LIME SODA PROCESS
Hint for solving numerical problems based on lime soda process.
1. All the impurities consuming lime and/or soda, are to be converted in equivalents per liter.
2. The impurities such as etc. should be ignored as they do not consume lime and soda.
3. or etc. should be considered as temporary hardness, due to bicarbonates of calcium and/or
magnesium and to be taken for lime calculations only.
4. The quantity of in terms of equivalent to be taken double, for calculations.
5. If or is present in water, then their equivalent per liter should be subtracted from soda
calculations.
6. Coagulants like sodium aluminate, aluminium chloride, aluminium sulphate etc. if used, their
equivalents per liter should be calculated and taken into account as,
For : subtract from lime
For : Add in lime and soda both

 Water sample was found to contain following salts.
Calculate the quantity of lime (85% pure) and soda (95% pure) for softening 50,000 liters of water.
Solution :
 Calculation of equivalent for impurities
Salt Qty Mol.Wt. Multiplication factor equivalent
per time
Requirement of Lime(L) and
/or soda(s)

55.5 111 50 S
20 60 Does not react with lime/soda - -
12.6 84 7.5 Add in L Subtract in S.
250 74.5 Does not react - -
48 120 40 L+S
2.2 44 5 L
43.8 146 30 L
2 55.8 3.58 L+S
10 133.5 7.5 L+S
Classwork problems
 Calculate the quantities of lime (85% pure) and soda (90% pure) required to soften 1,00,000 liters of hard
water containing following impurities.
 A sample of water was found to contain following salts :

Calculate the amount of lime and soda required for softening 75000 liters of above water.
 A water sample on analysis, gave the following data
Calculate the amount of lime (95% pure) and soda (90%) needed for treating 1 million liters of water.
 Calculate the quantities of lime and soda (905 pure each) required for softening 25000 liters of hard water
containing following ions/chemicals.
(May.2003)
 Calculate lime (80% purity) and soda (90% purity) required to soften 1 lakh liters of water containing the
following impurities.
 A water sample having hardness 250 ppm was softened by zeolite process. The exhausted zeolite bed required
50 liters of 15% solution for regeneration. Calculate the quantity of water softened using the zeolite bed.
Solution :
100 ml. solution  15 gms NaCl
1 liter solution  150 gms NaCl
50 liter solution  7500 gms NaCl
 gms equivalents of
 6410.256 gms equivalent
 6410256 mgs equivalent
Thus zeolite bed removed 6410256 mgs equivalent of hardness.
250 ppm hardness  1 liter of water
6410256 ppm hardness  liters of water
 25641.025 liters of water
25641 liters of water
 A zeolite bed got exhausted after softening 5000 liters of water. Hardness of water was 250 mgs
equivalent per liter. How many liters of 10% solution would be required to regenerate zeolite bed.
 The hardness of liters of water sample was completely removed by a zeolite softener. The zeolite required
80 liters of solution, containing 1000 mg/I pf for regeneration. Calculate the hardness of water sample.
ADDITIONAL
 Explain the theory of Lime-soda process with reference to the different functions of lime and soda. (5 Marks)
Lime-soda Process
Principle
In this method hard water is treated with calculated amounts of slaked lime, and soda ash
in reaction tanks, so as to convert hardness producing chemicals into insoluble compounds which are then removed
by setting and filtration.
Lime required for softening is calculated by using formula, as,

all in term of their equivalents.
Soda required for softening,
all in term of their equivalents.
Normally, about 10% excess of chemical are added in the reaction tanks to complete the reaction quickly.
(i) Reactions with lime
Lime reacts in following ways, during softening of water.
1. To neutralise any free acid present. For example
2. To precipitate iron aluminium salts, if any, as hydroxides.
(ii)Reactions with soda
Soda removes all the soluble permanent hardness due to calcium salts as
Natural water mainly have temporary hardness which is conveniently and economically removed by lime treatment,
as lime is cheap and removes temporary hardness efficiently without adding soluble salts in water. Thus, the net
outcome of lime-soda treatment is,
1. Reduction of soluble impurities imparting hardness to water by converting them to insoluble salt, and
2. Permanent calcium hardness by producing insoluble
However the acid radicals which are converted to their respective soluble sodium salts (e.g. )
remain in water. Water are traces of soluble salts such as cannot be used in higher pressure
boilers.
The chemical reaction taking place during lime-soda treatment are slow and precipitates of and
are fine and produce super saturated solution. As a result after deposition occurs in pipes, boiler tubes
etc. their diameters are reduced and the values get clogged and thus corrosion occurs. In order to avoid this,
following steps are taken :
1. Thorough mixing of chemicals and hard water.
2. Sufficient time allowed to complete reactions.
3. Accelerators i.e. substances that bring down the fine particles of precipitates e.g. activated charcoal are used.
4. Coagulants or flocculants i.e. substances which help in the formation of coarse precipitates are added e.g. alum.
5. Provision of proper sedimentation chamber for precipitates to settle, before filtration being carried out.
 Explain the terms :
1. B.O.D.
2. C.O.D.
What is their significance ?
Ans :-
(i) B.O.D.
Waste water contains two types of organic matter :
1. Biologically active or biologically degradable organic matter which can be oxidized by bacteria.
2. Biologically active inorganic matter which can’t be oxidized biologically.
Dissolved oxygen and organic matter present in water sample are closely related with each other. “The biochemical
oxygen demand (BOD) of water is measured of amount of oxygen required for the biological oxidation of organic
matter under aerobic conditions, at 20 C and for a period of five days.”
BOD is directly related to the extent of pollution in waste water and industrial effluent. The higher the BOD of
a sample the higher will be pollution caused by it. Drinking water should have BOD preferably less than 1 ppm.
Principle of BOD
The principle involved in the determination of BOD is :
1. The determination of dissolved oxygen (by Winkler’s method) initially and
2. Following a period of 5 days at 20 C.

The sample is maintained at this temperature for the period of testing.
Where Dissolved oxygen of diluted water sample immediately after its preparation.
Dissolved oxygen of diluted water sample after incubation for 5 days at 20 C, mg/L
Fraction of sample
…………(1)
Significance of BOD :
The higher the BOD of a sample the higher the amount of decomposable organic matter in the sample and
higher the pollution of the sample.
Therefore, BOD
1. Gives an idea about the extent of pollution at any time in the sewage sample
2. Helps in pollution control.
(ii)C.O.D.
“The amount of oxygen required by organic matter in a sample water for its oxidation by strong oxidizing agent is
known as chemical oxygen demand or COD of the sample”
Principle of determination of COD :
 A known volume of sample is refluxed with a known excess of solution in 50% , in the
presence of (Catalyst), and .
 is strong oxidizing agent, in acidic medium. It oxidizes the organic matter into and .
 Reaction
The unreacted dichromate solution is then titrated against std. FAS solution
using ferroin as indicator. At end point blue colour changes to wine red.
Significance of COD :
It helps in designing the water treatment plant
It helps in deciding the disposal of domestic effluents in various types of water streams.
 Explain theory, procedure and limitations of Zeolite process with the help of a neat diagram.
Ans. :
The name zeolite (Greek : Zein-boiling, lithos-stone) means boiling stone. The chemical formula od sodium
zeolite may be represented as,
(Where x = 2 to 10 and y = 2 to 6).
(Zeolite = hydrated sodium alumino silicate)
“Zeolite is hydrated sodium alumino silicate capable of exchanging reversibly their sodium ions for hardness
producing ions in water.” Zeolite are also known as permutits. Zeolites are of two types :
1) Natural zeolites
2) Synthetic zeolites.
1) Natural Zeolites
They are amorphous and non-porous. They are derived from green sands by washing, heating and treating
with NaOH. The natural zeolite are more durable and are as follows :

2) Synthetic Zeolites
They are porous and possess gel structure. They are prepared by heating together :
a) China clay, flesh par and soda ash and granulating the resultant mass after cooling.
b) Solutions of sodium silicate, aluminium sulphate and sodium aluminate.
c) Solution of sodium silicate and aluminium sulphate.
d) Solution of sodium silicate and sodium aluminate.
Synthetic zeolite have higher exchange capacity per unit weight.
Process of softening water by zeolite-permutit method
In operates alternatively as the softening run and the regeneration. During softening process the hard water
from top enter at a specified rate and passes over a bed of sodium salts is collected at the bottom of the cylinder and
is taken out from time to time.
The cations and are retained in zeolite bed and soft water rich in is
collected. After some time the zeolite bed gets exhausted, the softening run is discontinued and regeneration is
started. During regeneration process, the following three operations are carried out.
(a) Back washing.
(b) Salting (or brining) and
(c) Rinsing to get regenerated bed for reuse.
Limitations of zeolite process
1) Turbid water (contening suspended impurities) can note be admitted to the zeolite bed, otherwise it will block the
pores of zeolite and make zeolite inactive. Hence, suspended impurities must be removed before passing water
through.
2) If the water contains coloured ions such as , they must be removed first, because these ions produce iron
zeolite which cannot be easily generated.
3) Mineral acids if present in water, destroy the zeolite bed and therefore they must be neutralized with soda before
water being entered into zeolite plant.
 Give the brief account of reverse osmosis. [3 Marks]
Membrane technique (Reverse osmosis) :
Various membrane techniques are available, which selectively separated the solutes or contaminents on the
basis of pure size. The types of membrane separation technologies include reverse osmosis, hyperfiltration,
ultrafiltration, etc. But reverse osmosis is commonly used.
Principle of reverse osmosis (RO) :-
The reversal of solvent flow, from higher concentration solution to lower concentration solution through a
semipermeable membrance, by applying an external pressure slightly higher than the osmotic pressure of higher-
concentration solution, is known as reverse osmosis. Normal osmosis process, is shown in Fig., where the solvent
flows from low concentration solution to higher concentration solution, through the semipermeable membrane, until
difference in water levels creates a sufficient pressure counteract the original flow. The difference in levels represent
osmotic pressure of the solution.
In the reverse osmosis, we apply external pressure on the higher concentration solution slightly higher than its
osmotic pressure. The flow of solvent takes place in reverse direction i.e. from higher concentration solution to lower
concentration solution, through the SPM. Thus in RO, we separated water from its contaminants rather than
contaminants from water.

Method:
Sea water or water polluted by ionic pollutants, is filled in reverse osmosis cell. A pressure of 200-800 psi is
applied on it to force the solvent to pass through SPM. (SPM has such porosity that it allows only molecules to
pass through and higher sized ions/molecules are prohibited from passing).
Membrane consist of a polymeric material film made of proper porosity, from material like acrylic,
polyamides, aramids etc.
Advantages of Reverse Osmosis Over Conventional Processes.
1) Compared with other conventional water treatment processes, reverse osmosis has proven to be the most efficient
means of removing salts, chemical contaminants and heavy metals, such as lead, from drinking water.
2) For waters with total dissolved solids of 200 or more, reverse osmosis is less expensive than ion exchange.
3) Even at total dissolved solids of less than 200, it is preferred over ion exchange for removal of silica and organics.
4) Compared with distillation, reverse osmosis use only a fraction of the total energy and does not have high
temperature problems or scaling and corrosion.
5) Today reverse osmosis systems have proven to be the most economical and efficient means of improving the quality
of water.
6) Simple to Operate and Maintain
7) Reverse osmosis systems come assembled, factory tested and in ready-to-operate condition. They are designed for
efficiency and are simple to operate and maintain.
8) Besides regular monitoring and periodic membrane cleaning, membranes need to be changed every one to three
years depending on water quality, size of the system and pretreatment.
9) Pumps also require routine maintenance.
 Short note : Activated sludge method to control water pollution (5 Marks)
 Sewage contains mineral and inorganic matter in suspension and in solution. It also contains living organism, some
of which may be dangerous.
 Hence, treatment of sewage has to be carried out. These treatment processes can be classified into the following
categories :
1. Preliminary treatment 2. Primary treatment
3. Secondary or biological treatment 4. Dis-infection.
1. Preliminary treatment
Waste water contains floating suspended solids such as rags, wood, metal, plastic, etc. these have to be
removed as they interfere with the treatment process of mechanical equipments. In the preliminary treatment, these
suspended impurities are removed.
2. Primary treatment
Primary treatment to sewage mainly consists of the sedimentation process to remove suspended organic
solids. Chemicals are sometimes added in primary clarifies to assist in the removal of finely divided and colloidal
solids or to precipitate phosphorous.
3. Secondary or Biological treatment
In this category, processes such as filtration or activated sludge process are included. Filtration is done in
contact beds or intermittent sand filters or trickling filters. It removes finely divided suspended matter. In the
activated sludges process, the sewage is biologically treated.
A part of the digested sludge is added to the raw sewage together with oxygen which promotes coagulation of
the suspended and colloidal matter. The matter which settles down at the bottom after treatment is called sludge and
the liquid is called effluent.
The sludge is disposed off in many ways such as drying beds, dumping into sea, etc.

natural drainage or sea. Stages in sewage treatments are shown in Fig.
Trickling filters consist of circular beds, 2-5 m high, filled with porous lumpy materials, e.g. hard coke.
The waste is poured on the filter bed with the help of rotator sprinkler. As the waste water percolates the filter bed,
the aerobic grow using the organic matter in the sewage as their food. It is necessary to maintain highly aerobic
condition.
The organic matter undergoes biological oxidation due to these bacteria and the treated water is collected.
Yield of this method is normally nearly 90% BOD. The process is comparatively very fast, if the aerobic condition is
maintained. Second precaution to maintain the speed is the regular recirculation of the effluent so that filter does not
get choked due to excess bio-film growth taking place.
4. Disinfection
After the secondary or biological treatment the effluent free from sludges is subjected to disinfection. It is
chlorinated to kill the bacteria which may remain in the effluent of sewage. Though activated given/required by
water depend entirely upon the chemical analysis of water.
The severity of pollution is the sole criteria to choose one or more steps in combination to treat water, and the
end use of water also plays role. If the water is only to be safely disposed off, then the treatment steps are chosen
accordingly and vice versa.

CHAPTER-3 LUBRICANTS
“ The substances used to reduce the wear are known as lubricants ”
 Friction is nothing but, “ the force of resistance to the relative motion of two third surfaces in contract
” and co-efficient of friction if, “ the ration of force of frication to the applied force or load ”. Thus,
Coefficient of frication =
Frictional resistance
pplied force or load
 Here, if lubricating substances are applied on the moving surfaces, the friction reduces, and thereby
wear also gets minimized.
 Lubricants and Lubrication
[may.2003, Dec.2006, Dec.2007]
 The lubricants are defined as, “ the chemical substances which reduce friction between two sliding
/moving metal surfaces and thereby reduce wear and tear of machines. ”
 The lubricant keeps the two surfaces apart, thus the frictional resistance reduces. This helps is
reducing the destruction of material.
 Lubrication is nothing but “ a process by which wear gets reduced, with the use of lubricants. ”
 Functions of Lubricants
[Dec.2001, May.2004, May.2005, May.2008]
1. Lubricant reduce friction, wear and tear of surfaces
2. Lubricants reduce wastage of energy, and thereby increases efficiency of machines.
3. Lubricants act as coolants, thereby avoiding loss of energy. They reduce the frictional heat, thereby
controlling expansion of metals. It helps to maintain shape, size and dimensions of metal parts in
contact.
4. Lubricants reduce the wastage of power, e.g. in internal combustion engines, the lubricant applied
between the piston and the cylinder acts as a coolant.
5. Lubricant acts as a sealant, as it does not allow the escape of gases from engine under high pressure.
6. Lubricant prevents the attack of moisture on machine surface. This helps to control corrosion of the
moving machine parts.
7. Lubricants also help as clearing agent, because they have the tendency to wash off solid particles
produced due to combustion or wear. Thus with the presence of lubricants such particles are
transported away from the sliding surfaces. This helps to control corrosion of the surface.
8. If two metal surfaces in contact are different in material, i.e. one metal is harder than the other metal,
then the harder metal is sliding over the surface of a less hard (soft) metal, the coefficient of friction is
usually small and vice-versa.
9. The mechanism of lubrication is nothing but, “application of lubricant on sliding/moving surfaces and
its action towards reducing frictional resistance”.
 Fluid Film or Thick Film or
Hydrodynamic Lubrication
[May.2002, May.2003, Dec.2003,
Dec.2004, Dec.2006, May.2007]
 In this type of mechanisms, a liquid lubricant
with high velocity (generally vegetable/mineral
or blended oils) is applied in the form of thick
between two moving surfaces. The film is at
least 1000A thick.
 Such film helps to avoid surface to surface
contact of moving surfaces. The hydrodynamic
lubrication helps to reduce the coefficient of friction to about 0.001 to 0.03, which is much lower as
compared to that for unlubricated surfaces (0.5 to 1.5).

 The mechanism of hydrodynamic lubrication can be better understood by considering the operation of
a journal bearing. Refer Fig. The bearing consist of shaft rotating at a fair speed, with moderate hold.
 The lubricant is applied in annular space. When journal bearing is stationery the two surface remain
in contact, but as the shaft (journal) begins to rotate, the film of lubricant also rotates between the two
metallic surfaces.
 Due to the presence of thick oily layer, all the asperities of the metal surfaces are filled up and a
pressure is developed which practically keeps the two surfaces away from each other, thereby
reducing wear. The motion is smooth as the resistance to the motion is restricted amongst the
particles of lubricant.
 To achieve best result in hydrodynamic lubrication, the lubricant chosen should posses an adequate
viscosity, so that an uniform layer of lubricant is always maintained between the two moving
surfaces.
 It is complicated to choose an appropriate lubricant for this purpose, because oils have a tendency to
change viscosity with temperatures.
 Thus an oil having adequate viscosity at low (room) temperature, i.e. when machine is at rest, may
show a fall in viscosity when the machine gets heated during operation at running temperature.
 Even during different seasons, it is difficult to maintain the viscosity due to fluctuating temperatures,
especially if vegetable oils are used. Hence, the blended oils are more suitable.
 The hydrocarbon lubricant blended with long chain polymers, are found to be able to maintain
adequate viscosity at working temperatures. Such
blends may result in formation of gums or lacquers
under operating conditions because of the presence
of unsaturated compounds in traces, which have
oxidizing tendency.
 To overcome this problem, generally antioxidants
e.g. aminophenols are added into blends. Further,
these lubricants also tends to undergo
decomposition under working conditions resulting
into formation of carbon particles.
 Such carbon particles can be normally kept floating
in suspension in lubricating oil, by using
organometallic compounds (detergents).
 Hydrodynamic lubrication mechanism is used to
lubricate machine parts in sewing machines,
clocks, watches, scientific instruments, etc.
 Thus this mechanism is useful in machines where
load is low and speed is not very high.
 Thin Film or Boundary Lubrication

[Dec.2001, Dec.2007]
 This type of mechanism is useful certain working conditions of machines, such as :
(i) If viscosity of liquid lubricant (oil) is low,
(ii) The machine is to be operated at comparatively low speed
(iii)During operation of machine, a shaft moving from rest at fixed intervals or
(iv)The machine is operated under high load.
 A continuous thick film of lubricant cannot persist in between two sliding surface under such working
conditions. Hence, to reduce friction in such machine a thin film of lubricating oil is introduced in the
clearing space of the moving surfaces.
 This film gets adsorbed on metal surface due to physical or chemical or both the forces and it is
retained there. The coefficient of friction falls to the extent of 0.05 to 0.15 and load on the machine is
carried by the adsorbed thin film between the sliding surfaces.
 Intermittently the layer of lubricant is checked, so that the machine surfaces remain protected from
friction. The lubricants generally applied are the soaps of vegetable or animal oils, as they possess a
great tendency of adsorption on surfaces.
 These soaps get attached to surface either by physical force or by chemical forces and form a very
thin film which covers all irregularities of metal surface, thereby reducing the frictional wear.
 The soaps are suitable at moderate temperatures, But at high temperatures, they get decomposed.
Here, these are not suitable to used in internal combustion engines. In such cases, mineral oils
blended with fatty acids are used, because the thermal stability of mineral oils is high.
 Other substitutes are solid lubricants such as, graphite or molybdenum di-sulphides, either alone or
their stable suspension in oil, which is also suitable. These suspensions or solids form a thin film on
metal surfaces which can bear load as well as high temperatures.
 In short, the lubricants possessing :
1. High viscosity index,
2. Resistance to oxidation
3. Stability at elevated temperature,
4. Adequate oiliness, and
5. Low pour-point are most suitable for boundary lubrication.
 e.g. Mineral oils blended with vegetable and/or animal oils, solid lubricants such as Graphite or
Molybdenum di-sulphide.
 The machine where boundary lubrication is commonly applied are, gears, rail axle boxes, tractors,
rollers etc.
 Extreme pressure lubrication
[May.2002, May.2005, Dec.2005, May.2006]
 At working conditions where sliding/moving surfaces are under high pressure and high speed, the
machine surfaces normally attain slightly higher temperature.
 Under such working conditions, the liquid lubricant may not stick to the surfaces and it may also
decompose at that temperature, losing its lubricating capacity. There might be loss of lubricant due to
vaporization.
 To satisfy the requirement of lubricant under such extreme conditions. Generally mineral oils with
special additives are used. Such additives used to improve specific characteristics of lubricating oil
are known as extreme pressure additives. The substances under this category should have a tendency
to adhere on metal surfaces with greater local forces of attraction to form thicker film which sticks to
the metal surface and retain in place for longer duration.
 Such a film of lubricant should be able to withstand high temperature and pressure. Substances such
as chlorinated esters, sulphurised oils or phosphates (like tri-cresylphosphate) are commonly used.
 The metal underlying the film of lubricant reacts with these additives and form metalchlorides,
sulphides or phosphides. Such metal compounds possess very high melting points.
 Hence, the film of lubricant remains on the surface of metal providing adequate lubrication, under
such extreme pressure and extreme temperature working condition.
 Such additives give good results on metals like iron, but are not suitable for use on chemically insert
metal surfaces. e.g. silver, copper or titanium.

 In addition to these additives, colloidal suspension of solid lubricants in oil or resin have been found
most suitable for extreme pressure-temperature lubrication.
 The machines in which E.P.T. lubrication is applied are, cutting tools, rock crushing machines, wire
drawing machines etc.
 CLASSIFICATION OF LUBRICANTS
On the basis of physical state, the lubricants are classified as follows :
 Viscosity and Viscosity Index
[May.2000, May.2004, May.2006]
 Viscosity can be defined as, the property by virtue of which a liquid or fluid (oil) offers resistance to
its own flow.
 Viscosity Index can be defined as rate of exchange of viscosity with respect to temperature.
 Oils becomes thin on heating i.e. their viscosity falls/decreases. If the decrease in viscosity is rapid
the oil is said to have a low viscosity index and vice-versa. A good lubricant should have high
viscosity index.

 Viscosity and viscosity index are related to molecular weight of oils. Generally oils with higher
molecular weight slow higher viscosity. For an ideal lubricant viscosity. For an ideal lubricant
viscosity should be appropriate.
 Measurement of viscosity of an oil is carried out using an apparatus called as viscometer. In
commonwealth countries, Redwood viscometers are used while in U.S.A Saybolt viscometer is used.
 The viscosity of oil expressed in terms of seconds of the respective apparatus; because the viscosity is
measured as time taken for a foxed volume of oil to flow through orifice of the oil cup of the
apparatus. Thus if it is a Redwood viscometer, then viscosity is say x Redwood seconds and so on.
 Redwood Viscometers are of two types as Redwood viscometer number 1 and Redwood viscometer
number 2, the former is used to determine viscosity of thin oils i.e. which possess low viscosity, while
the latter one is used for thicker (viscous) oils.
 In our country Redwood viscometer number 1 is commonly used, which is shown in fig.
Construction of Redwood Viscometer :
1. Oil cup
 It is silver plated cylinder, open at top; 90mm in height 46.5mm in diameter. The agate jet with bore
of diameter 1.62mm and 10mm in length is fitted at the bottom of oil cup.
 The jet can be opened or closed with a valve rod, which is a small silver plated brass ball, fixed to a
long stout wire, which helps to use this valve rod. The cup at its upper end is fitted with a pointer,
which a pointer, which indicates the level up to which the cup should be filled with oil.
 The oil cup is provided with a lid having an opening for thermometer. This thermometer is used to
record the temperature is used to record the temperature of oil.
2. Heating bath
 Surrounding to the oil cup a cylindrical copper container is fitted. This serves as water/heating bath.
The water is to be filled in this cylinder from its opening at top.
 After the use of viscometer hot water is removed from hot water outlet which is attached at the left
side of bottom of this container.
 At the right side of bottom, a side tube is provided which is used for heating the oil. Now-a-days
electrically heating viscometers are also available.
3. Stirrer
 Outside the oil cup a stirrer with four blades is provided, so as to heat the water uniformly.
 It is also provided with a shield which prevents the splashing of water during operation. Thus water
does not enter the oil cup.
4. Spirit level
 The lid of oil cup is provided with spirit level for vertical leveling of the jet.
5. Levelling screws
 The three legs of the apparatus are provided with leveling screws. These help to level the apparatus.
6. Kohlrausch flask
 It is a wide mouth flask measuring definite quantity of oil, (generally 50 ml.) which is shown on its
neck as a circular mark.
WORKING OF REDWOOD VISCOMETER
 The oil cup is cleaned and leveled.
The oil is filled upto the pointer mark.
The agate jet is closed with valve rod.
The water bath is filled with water at
room temperature.
 A clean Kohlrausch falsk is arranged
under the agate jet. The temperature of

the oil is record. The valve rod is shifted rod is shifted to open the agate jet so that oil starts flowing
out of oil cup.
 The stop watch is quickly started at this moment. The time in seconds is recorded for 50ml. of oil to
flow out. The agate jet is closed with valve rod. The coil is again filled up to the pointer.
 A burner is arranged under the side tube provided for heating the water bath and the oil. When the
thermometer shows that the temperature is 10 C above the room temperature, 50ml of oil collected in
flask in the similar way as was done at room temperature.
 The time in seconds is recorded. Similarly readings of time measurement are taken at 20 C, 30 C, 40
C, 50 C. i.e. at higher temperatures. Similarly with falling temperatures also the procedure can be
repeated.
 Then a graph of temperature v/s time (Redwood Seconds) is plotted. Refer Fig.
 It is a linear curve, because as the oils on heating become thin, their viscosity decreases and hence the
time taken for definite quantity of oil to flow out of the agate jet reduces.
 Significance of viscosity and viscosity index :
A lubricating oil selected for a job should have viscosity index as high as possible. This helps
in achieving desired results to control wear and tear of machine parts. The study also helps to decide
about the addition of blending agents to improve the property of lubricating oil.
 Saponification Value
[may.2000, Dec.2006, May.2007, Dec.2007]
 Saponification value of an oil can be defined as, the number of milligrams of potassium hydroxide
required to saponify one gram oil.
 Saponification value is the characteristic property of vegetable/animal oils, and not of
mineral/synthetic oils. This is because mineral/synthetic oils do not undergo saponification.
Saponification is nothing but alkaline hydrolysis of pure oil giving soap and glycerol.
 The vegetable/animal oils are triglycerides of mixed fatty acids. The fatty acids normally found
present in these oils are from to and many oils have been higher fatty acids.
 The mixed fatty acids are of saturated as well as unsaturated nature. For example, capric ( ),
caprilic ( ), caproic ( ), lauric ( ), myristic ( ), palmitic ( ), stearic ( ), etc are saturated
fatty acids. The general empirical formula of these acids is .
 The most common unsaturated fatty acids are oleic [ ] linoleic [ ], linolenic [ ] acids. All
these fatty acids are present in oils in the form of their triglycerides. During saponification, on
treatment of oil with aqueous alkali (KOH), the soaps are formed and the potassium salt of glycerol is
released.
 Determination of saponification value of an oil.
 A known quantity (W gms) of oil is mixed with known excess of alcoholic KOH solution (0.5 N). the
mixture is shaken very vigorously and allowed to stand for nearly 24 hours at room temperature.
Alternatively the mixture is refluxed for about 2 hours, on water bath, using water condenser.
 The fatty acids form potassium salts (soaps) and glycerol is released.
 In the above reaction the oil consumes KOH. At the end, the unreacted KOH is titrated using dil. HCl
(0.5 N). The blank reading is taken which can be used in knowing the quantity of alc. KOH
reacted/consumed.
 The amount of unreacted KOH is known from amount of HCl consumed; thereby the quantity of
KOH consumed can be calculated. Saponification value is calculated using formula,
Saponification value =

Amount of KOH consumed (Blank – Back)
Normality of O 0. N
eight of oil taken gms.
The saponification value is expressed as milligrams of KOH.
 Acid Value
[May.2000, Dec.2004, May.2008]
 Acid value is defined as the number of milligrams of KOH required to neutralize free fatty acids
present in one gram of oil.
 It is essential to determine the content of free acids in an oil ,because these acids if present even in
small quantity, harm machines during lubrication. The lubricating oils, mineral or vegetable/animal
based, generally possess long hydrocarbon chains or fatty acids as glycerides.
 The mineral oils on prolonged exposer to from air or continuous rise or fall of temperature in
working conditions undergo clearing and get oxidized by air.
 The vegetable/animal based oils contain fatty acids in combined form as triglycerides of mixed fatty
acids. The unsaturated sites in fatty acids tend to absorb on exposure to air, and form carboxylic
acids.
 Thus the absorption of and thereby formation of carboxylic acids affects the quality of oil. Such an
oil becomes unsuitable for lubrication, because acids affects the machine parts. Thus ideally acid
value should be minimum, to make oil suitable.
Determination of acid value of an oil
 The oil sample is weighted (W gms, ideally 1 gm) and mixed with absolute alcohol (50 ml for 1 gm
of sample ideally). The mixture is warmed for 10-15 minute on water on water bath.
 The free fatty acids separate out from oil. The mixture is then titrated against standard 0.1 N KOH
solution, using phenolphthalein indicator. The quantity of KOH solution is noted as ml. the acid
value is then calculated as,
Acid value =
uantity of O ml normality of O
eight of oil gms
Unit of acid value is mgs of KOH
Significance of acid value
The determination of the acid value can help us know the suitability of the lubricating oil.
Higher the acid value, more the corrosion of machine surfaces, more wear and tear, more
maintenance cost for machines.
PROBLEMS
 5 gms of a vegetable oil was saponified using excess of alcoholic KOH [0.5 N]. The mixture required
15.0 ml. of 0.5 N HCl while blank titration required 45.0 ml of same HCl. Find the saponification
value of the oil.
Solution :
Given Weight of oil = 5 gms
Blank titration reading = 45ml. 0.5 N HCl
Back titration reading = 15ml 0.5 N HCl
Thus, volume of 0.5 N KOH required by the oil for saponification in terms of 0.5N HCl = 45 –
15 = 30 ml.
olume of O consumed Normality of O
eight of oil in gms.

Ans. : Saponification value of oil = 168 mgs KOH
 6 gms of an oil was saponified with 50 ml 0.5 N alcoholic KOH. After refluxing for 2 hrs the mixture
was titrated by 25ml of 0.5 N HCl. Find saponification value of oil.
 1.55 gm of an oil is sponified with 26ml of N/2 alcoholic KOH. After refluxing the mixture, it
requires 15ml of N/2 HCl. Find saponification value of oil.
[Dec.2003, 3 marks]
 16 gm of blended oil was heated with 50 ml KOH. This mixture then required 31.5 ml of 0.5 N HCl.
50 ml KOH required 45 ml 0.5 N HCl. Find % cottonseed oil, if saponification value = 192 mg.
[Dec.2005, 6 marks]
Solution :
Given
Weight of blended oil = 16 gm
Amount of KOH = 50 ml
Normality of HCl = 0.5 N
Amount of HCl = 31.5 ml
Saponification value = 192 mgs
% cottonseed oil = ?
To find : % cottonseed oil in blend
50 ml KOH = 45 ml 0.5 N HCl
Normality of KOH = 0.45 N
∵ Weight of blended oil = 16 gm
Weight of cottonseed oil = 16 – x gm
Now, saponification value =
lank – ack N
1 -x
Blended oil contains castor oil and petroleum oil.
petroleum oil has saponification value always zero.
Let us calculate saponification value of the blended oil.
olume of O
eight of lend
=
Saponification-value of blend = 21.26 mgs of KOH
castor oil =
aponification value of blend
saponification value of castor oil
=
= 11.074 %
Ans. : % of castor oil in blend = 11.074 %

 1.55 gram of an oil is saponified with 20 ml of alcoholic potassium hydroxide solution. After
refluxing the mixture, it requires 15ml of HCl solution. Find saponification value of oil.
[May.2008, 3 marks]
 What are blended oils ? How are they superior to vegetable and mineral oils ?
[2 marks]
Ans. :
Blended oils
Blended oils are normally made by using vegetable/animal/mineral oils. The blends can be
made in such a way that the characteristics/properties of lubricant get improved to suit the service
conditions of machinery. Blending is essential because no single pure lubricant serves satisfactorily.
Blending agents are used to improve properties such as viscosity index, oxidation stability, oiliness,
pour, flash point etc. Other types of additives are corrosion/abrasion inhibitors, antifoaming agents,
emulsifiers etc. in addition to this, certain additives are added so that extreme pressure conditions of
machineries can also get suitable lubricants.
The table shows the substances/compounds commonly used to improve the properties of the
lubricants i.e. of blend.
Property Substances/Compounds
Oxidation stability improves Aromatic amine, phenols, organic sulphides
phosphides etc. they retard oxidation of oil, but they
themselves get oxidized preferentially. e.g. in
internal combustion engines where lubricants tend to
get oxidized.
Corrosion/Abrasion stability improves Organic compounds of phosphorous or antimony.
They form a layer between the sliding surfaces
thereby not allowing contact between the surfaces.
Foam preventors. Glycols or glycerols. Phenols or compounds of
naphthalene. Pour point depressants.
Viscosity index improvers. High molecular weight organic compounds e.g.
haxanol.
Viscosity improvers. Polystyrenes, polyesters etc. They act as thickeners.
Extreme – pressure / temperature
additives
Organic phosphorous / sulphur / chlorine
compounds, fatty acids / esters, chlorinated waxes,
tricresyl phosphate, Vegetable oils etc.
Oiliness carriers Vegetable oils, fatty acids / amines.
Cloud / pour point depressants Waxes, alkylated naphthalenes and phenols.
Antiwear additives Substances like tricresylphosphate, Zn-dialkyl di
thipphosphate.
Rust inhibitors Fatty acids, Aminophosphates.
 Explain any two of the following properties of lubricants :
1) Flash point and fire point temperature
2) Cloud point and pour temperature
3) Saphonification number
Ans. :
1) Flash point and fire temperature
Flash point can be defined as, the temperature at which the oil gives out enough vapours that
ignite for a moment when a small flame is brought near it. Fire point can be defined as, the
temperature at which the oil gives out enough vapours which burn continuously at least five seconds
when a small flame is brought near it.
The flash and fire points are very important properties of an oil, because these helps in
knowing the highest temperature upto which an oil can be used as a lubricant.
These constants are usually determined by using Pensky-Marten’s flash point apparatus.

2) Cloud point and pour temperature
Cloud point ccan be defined as the temperature at which the oil becomes cloudy or hazy in
appearance. Pour point can be defined as, the temperature at which the oil ceased to flow or pour.
These characteristic physical constants indicate the suitability of oils at lower temperature, or in cold
condition. The lubricating oils used in machines working at low temperatures, should have much
lower cloud and pour points than the working temperatures.
Otherwise, the lubricating oil may get solidified at working temperature and this may cause
jamming of the machine parts. This may affect the speed of the machine. The cloud and pour point of
oils with impurities are generally high, especially if waxes are present. Hence, it is essential to
remove wax like impurities from the oils during their extraction and purification.
Apparatus consist of a broad petridish/jar, which is used as a cold bath. The oil is taken in a
flat bottomed hard glass test tube. Two thermometers, are suspended, one in oil tube and other in
cooling mixture in jar to note the respective temperatures.
3) Saphonification number.
Saponification value of an oil can be defined as, the number of milligrams of potassium
hydroxide required to saponify one gram of oil. Saponification value is the characteristic property of
vegetable/animal oils, and not undergo saponification. Saponification is nothing but alkaline
hydrolysis of pure oil giving soap and glycerol.
The vegetable/animal oils are triglycerides of mixed fatty acids. The fatty acids normally found
present in these oils are form to and many oils have even higher fatty acids. The mixed fatty
acids are of saturated as well as unsaturated nature. For example, capric ( ), caprilic ( ), caproic
( ), lauric ( ), myristic ( ), palmitic ( ), stearic ( ), etc are saturated fatty acids. The
general empirical formula of these acids is .
The most common unsaturated fatty acids are oleic [ ], linolenic [ ] acids. All these
fatty acids are present in oils in the form of their triglycerides. During saponification, on treatment of
oil with aqueous alkali (KOH), the soaps are formed and the potassium salt of glycerol is released.
Significance of saponification value
The knowledge of saponification value helps to know the stability of oil in aqueous/alkaline
medium if in case machine parts face any such conditions.
Further it also signifies the composition of vegetable/animal oils, thereby helps to check the
suitability of oils for lubrication purposes. Drying property of oils which is harmful during lubrication
can also be checked.
E.g.
 What are lubricants? List
different functions of lubricants.
Ans. :
The lubricants are defined as, “the chemical substances which reduce friction between two
sliding/moving metal surfaces and thereby reduce wear and tear of machines.” The lubricant keeps
the two surfaces apart, thus the frictional resistance reduces. This helps in reducing the destruction of
material. Lubrication is nothing but “a process by which wear gets reduced, with the use of
lubricants.”
Functions of Lubricants
1) Lubricants reduce friction, wear and tear of surfaces.
2) Lubricants reduce wastage of energy, and thereby increases efficiency of machines.
3) Lubricants act as coolants, thereby avoiding loss of energy. They reduce the frictional heat, thereby
controlling expansion of metals. It helps to maintain shape, size and dimensions of metal parts in
contact.

4) Lubricant reduce the wastage of power, e.g. in internal combustion engines, the lubricant applied
between the piston and the cylinder acts as a coolant.
5) Lubricant acts as a sealant, as it does not allow the escape of gases from engine under high pressure.
6) Lubricant prevents the attack of moisture on machine surface. This helps to control corrosion of the
moving machine parts.
7) Lubricants also help as cleaning agents, because they have the tendency to wash off solid particles
produced due to combustion or wear. Thus with the presence of lubricant such particles are
transported away from the sliding surfaces. This helps to control corrosion of the surfaces.
 Explain any two of the following properties of lubricants :
Ans. :
1) Oiliness
Viscosity can be defined as, the property by virtue of which a liquid or fluid (oil) offers
resistance to its own flow. Viscosity Index can be defined as rate of change of viscosity with respect
to temperature. Oils become thin on heating, i.e. their viscosity falls/decreases. If the decrease in
viscosity is rapid the oil is said to have a low viscosity index and vice versa. A good lubricant should
have high viscosity index. Viscosity and viscosity index are related to molecular weight of oils.
Generally oils
with higher
molecular weights
show higher
viscosity. For an
ideal lubricant
viscosity should
be appropriate.
Measurement of
viscosity of an oil
is carried out
using an
apparatus called
as viscometer. In
commonwealth
countries,
Redwood
viscometers are
used while in
U.S.A Saybolt
viscometer is
used.
The
viscosity of oil is expressed in terms of seconds of the respective apparatus; because the
viscosity is measured as time taken for a fixed volume of oil to flow through orifice of the oil
cup of the apparatus. Thus if it is a Redwood viscometer, then viscosity is say x Redwood
seconds and so on. Redwood Viscometers are of two types as Redwood viscometer number 1
and Redwood viscometer number 2, the former is used to determine viscosity of thin oils i.e.
which possess low viscosity, while the latter one is used for thicker (viscous) oils. In our
country Redwood viscometer number 1 is commonly used, which is shown in Fig.
(ii) Acid value
Acid value is defined as the number of milligrams of KOH required to neutralize free fatty
acids present in one gram of oil. It is essential to determine the content of free acids in an
oil because, these acids if present even in small quantity, harm machines during lubrication.
The lubricating oils, mineral or vegetable/animal based, generally possess long
hydrocarbon chains or fatty acids as glycerides. The mineral oils on prolonged exposure to

O2 from air or continuous rise and fall of temperature in working conditions undergo
clearage and get oxidised by air.
The vegetable/animal based oils contain fatty acids in combined form as triglycerides of
mixed fatty acids. The unsaturated sites in fatty acids tend to absorb oxygen on exposure to
air, and form carboxylic acids. Thus the absorption of O2 and thereby formation of
carboxylic acids affects the quality of oil. Such an oil becomes unsuitable for lubrication,
because acids affect the machine parts. Thus ideally acid value should be minimum, to
make oil suitable.
Determination of acid value of oil
The oil sample is weighed (W gms, ideally 1 gm) and mixed with absolute alcohol (50 ml
for 1 gm of sample ideally). The mixture is warmed for 10-15 minutes on water bath. The
free fatty acids separate out from oil. The mixture is then titrated against standard 0.1 N
KOH solution, using phenolphthalein indicator. The quantity of KOH solution is noted
ml. the acid value is then calculated as,
Acid Value
uantity of O ml normality of O
eight of oil gms
Unit of acid value is mgs of KOH
Significance of acid value
The determination of the acid value can help us know the suitability of the lubricating
oil. Higher the acid value, more the corrosion of machine surfaces, more wear and tear, more
maintenance cost for machines.

CHAPTER-4 : ENERGY
 Name the different renewable and non-renewable sources of energy. Distinguish between conventional
and non-conventional energy.
Ans. :
1. Conventional (Non-renewable) sources
e.g. Fossil fuels – coal, nuclear fules
2. Non-conventional (renewable) sources
e.g. solar energy, wind energy etc.
 What is fuel cell? Explain the principle and working of hydrogen – oxygen fuel cell.
Ans. Fuel cells convert the chemical energy produced by a chemical reaction into usable
electric power/electrical energy. Fuel cells produce electricity as long as fuel (hydrogen) is
supplied, and the charge is not reduced/lost. Fuel cells produce direct current (DC) power, not
alternating current (AC) power similar to a battery.
Operation of Fuel Cells
A fuel cell is an electro-chemical device in which the chemical energy of fuel is
continuously converted into electric energy. This conversion of energy takes place at constant
pressure and temperature.
The important feature of a fuel cell is that the fuel and the oxidant are combined in the form of
ions.
e.g. hydrogen ( ) – Oxygen ( ) called hydrox fuel cell.
The main component of a fuel cell are :
1. Anode comprising of fuel.
2. Cathode comprising of an oxidant, (Which is also a fuel material)
3. An electrolyte (a solution: of S04 for acidic fuel cell and KOH for alkali fuel cells).
4. Container with inlets and outlets for to
5. Separators.
6. Sealing material.
Fig. represent the schematic diagram of an alkaline fuel cell, using
1. Hydrogen as fuel,
2. Oxygen as oxidant, and
3. Alkaline solution of KOH as
electrolyte.
A hydrox ( ) fuel cell
(Alkaline Fuel Cell)
Workings
1. The electrodes are connected through an external circuit as shown in Fig.
2. The anode is supplied with Hz gas as fuel at a certain pressure and the cathode is supplied with
O2 as oxidant at same pressure.
3. These gases pass through the respective electrodes and bubble through the electrolyte solution.
4. The electrochemical reactions take place between gases, electrodes and electrolyte to come in
contact
5. The electro-chemical reactions being generally slow, it is a common practice to use a catalyst to
accelerate the reaction
6. Platinum is the best catalyst but costly. Other less expensive catalysts like nickel and silver are
used.
 Write short note on : Alkaline batteries.
Ans. : Alkaline storage batteries are secondary batteries in which potassium hydroxide (alkaline
electrolyte solution) is used as the main electrolyte. Most of these battery systems use nickel

oxyhydroxide (NiOOH) as the positive active material because of superior charge-discharge cycle
characteristics and Long life.
Example: Nickel cadmium (Ni-Cd) system, Nickel-metal hydride (Ni-MH) based
batteries, Ni-Hydrogen, Nickel-Iron battery.
There are two types of alkaline storage batteries presently in use
(i) "open" type which permit gases to be exchanged with the medium,
(ii) "sealed" type which have a valve and no exchange with the outside medium in normal
operation. e.g. Nickel-cadmium and Nickel-metal hydride storage batteries.
These are small, light weight and provide high output densities and are capable to boost
charging and high-current· discharging. They used as power sources for various devices and
apparatuses both in portable and industrial.
e.g. cellular phones and notebook computers, electric cars, or hybrid vehicles.
These are highly immune to overcharging and over discharging. It has therefore been used for
electronic products in which a large storage capacity and high charge/discharge efficiencies are
required. Their excellent capacity and reliability, nickel metal hydride batteries are considered
to be most promising for electric power sources of electric tools and electric vehicles which
require charging and discharging at high-rate.
 Give the composition of biogas. Describe the method for production of biogas from animal
waste.
Ans. : Biomass Conversion
1. Thermochemical processes
-Combustion
-Gasification
-Pyrolysis
2.CheIrucal processes
-Various chemical processes
e.g. Transesterification of oil to get biodiesel
3. Biochemical processes
-Anaerobic digestion
-Fermentation
-Composting
(I) Thermal conversion by combustion
Combustion is a process in which any flammable material undergoes burning in the
presence of air or oxygen.
 Basically combustion is nothing but 'oxidation'.
 The heat generated can be used directly for the output. e.g. Water heating.
Combustion of biomass specifically involves the elements such as carbon, hydrogen,
which undergo combustion to form to .
e.g. Cellulose, Hemicellulose etc.
Biomass, may contain other elements such as, Sulphur (S), Phosphorous (P), Nitrogen
(N), Potassium (K), Sodium (Na), Silicon (Si), Heavy metals, Alkali metals etc. All these metals,
being active, participate in combustion, forming their respective compounds.
Such products draw concern as, these might contribute to pollution. Hence are required
to be treated further for removal.
Applications of combustion
(1) In co-generation, which is simultaneous generation of heat and electricity.
Recent development also involves refrigeration process as well simultaneously known as "Tri-
generation".
This is called as CHP Le. "Combined heat and power".
CHP is mostly advisible in case,
(a) Space heating requirement exists near the generator. (b) Local areas require low temperature
water for use.
(2) In co-firing which is a process of replacing fossil fuel partially (when fed into any power
station or boiler) with any other alternative renewable (e.g. Carbon lean) source
This application is used only in coal fired power station.
More development in the technology of co-firing is in progress.

(II) Thermal conversion by Gasification
When a carbon source like biomass (or coal or natural gas) is broken into the products
like ,CO2, CO and /or CH4 by subjecting it to partial oxidation, the process is named as
"Gasification".
Types of Gasification
There are two types of gasification,
(a) Low temperature gasification (700-1000°C)
This process gives the product gases where high % hydrocarbons are present.
(b) High temperature gasification (1200-1600 )
This process gives the product gases where high % of CO and are present.
Application
Gasification can be used for
(a) Generating steam
(b) Heating water for different processes.
(i) Thermal conversion using pyrolysis
Pyrolysis is a process of thermal decomposition in the absence of oxygen. The products obtained
can be gaseous or liquid.
It is temperature dependent and there are following two types of pyrolysis.
(a) Low temperature pyrolysis.
(b) High temperature pyrolysis.
Low temperature pyrolysis i.e. 400 C, proceeds slowly. about 500
High temperature pyrolysis i.e. 500 or above, proceeds fast.
Unique feature of this process, is, if temperature kept around 500 C and vapour residence time is
maintained low i.e. 1 second or less, the product is bio-oil, followed by other gaseous products.
 Bio-oil obtained is,
(a) Dark brown in colour,
(b) Optimum viscosity for oil to be mobile
(c) Low heating value (as compared to conventional fuel oil)
 Bio-oil thus obtained can
(a) Directly burned
(b) Modified to match properties to other fuel oils,
(c) Gasified or co-fired.
(II) Chemical conversion
There are many chemical processes to get biomass converted into energy source. e.g.
Transesterification of vegetable oil to give biodiesel. Vegetable oils, though combustible, pose problem in
their direct use as fuel. This is because of their chemical composition where fatty acids are in triglyceridic
form, i.e. one molecule of glycerol is combined to three molecules of fatty acid chain.
They are highly viscous as compared to mineral oils, and hence need to be modified to make them
suitable for use as fuel in vehicles etc. Hence, vegetable oils or animal fats are transesterified. In this
process, the oil is reacted with ethanol or methanol to convert the triglyceridic esters to monoesters each
with one fatty acid chain known as fatty acid methyl esters which itself if “Biodiesel”
The suitability of the process depends upon,
(a) % of standard fatty acids.
(b) Melting point of fatty acids etc.
Few oils such as palmoil, soyabean oil, rape seed oil are found suitable for modification by this
method. Biodiesel thus produced can be used directly or as blend with petroleum (generally 5% biodiesel,
95% fossil diesel).
(III) Biochemical conversion
This technology makes use of enzymes or bacteria and other micro-organism to break down bio-
mass.
The technique involves,
(a) Anaerotric digestion.
(b) Fermention
(c) Composting.
Biochemical conservation : By Anaerobic digestion.
In Anaerobic digestion, as term indicates, anaerobic bacteria are used, which attack

organic matter of biomass, there by breaking it to form mainly a gaseous product. This gas is
known as 'biogas'. Main chemical component of 'biogas' is methane (CH4). Where as in low
proportion CO2 is produced. This process is used to process sewage since very long time, where
apart from above gases, solid residue similar to 'compost and some liquid product are also given
out, which are suitably used as fertilizer
In marshy places, such a process automatically also occurs, producing foul smelling
gas which is commonly called as "Marsh gas" or "Landfill gas".
Methane gas produced can be used
(a) Directly for producing heat
(b) In electricity generation.
Biochemical conservation by Fermentation.
Fermentation is a process known for decades, commonly used for brewing and wine making,
involving conversion of sugar to alcohol (ethanol). From biomass, bioethanol is obtained, using
enzymatic hydrolysis of biomass to convert into saccharides (which are fermentable). Bioethanol
produced can be used as blend with fossil petrol in range of 5 to 10%, as fuel.
Biochemical conservation by composting
It is similar to Anaerobic digestion, where the only difference lies in,
(a) In AD slurry is used
(b) In composting dry material is used.
Hydrogen as a fuel
Hydrogen is one of the best secondary source of energy, it is obtained by splitting the molecule of
water by using other energy such as nuclear or solar.
It is also obtained by electrolysis.
 What are fuel cells? List the advantages of fuel cells over
conventional power plants.
Ans. : Fuel cells convert the chemical energy produced by a
chemical reaction into usable electric power/electrical
energy.
Fuel cells produce electricity as long as fuel
(hydrogen) is supplied, and the charge is not reduced/lost.
Fuel cells produced direct current (DC) power, not
alternating current (AC) power similar to a battery.
 What is solar energy? Explain the working of solar heating
system using flat plate collectors.
(6 Marks)
Ans. : The electromagnetic radiation from sun are known by “Solar Energy”.
Flat plate solar collector (Solar heater)
The device works on principle of "perfect black body" in which heat absorbing capacity
and tendency of a black surface is exploited to achieve benefits for humans. "Perfect black body"
can be defined as! "the surface which can absorb all the radiations incident on it, without
reflecting or transmitting a portion of it".
The coefficient of absorption for perfect black body is unity. The coefficient of reflection
and transmission for PBB is zero.
Construction
1. It consist of black surface to absorb all radiant heat from sunlight.
2. The black surface is covered by plastic or glass serving as insulator, preventing the escape of
heat. Thus it increases efficiency of device.
3. There are tubes embedded in the black surface, carrying water, which get heated due to the heat
absorbed.
4. The air passing through the area between black surface and plastic/glass cover also gets heated,
which is utilised in raising the temperature of surrounding, creating warmth and comfort in
winter/cold countries.
5. Thus at almost negligible cost, the hot water can be made available and also space
warming is fulfilled.
6. These devices are now very common in colder countries, which has solved the problem of
environmental pollution and also of the expenditure on any other energy source

 Write short note on : Photovoltaic cell
Ans. : Photo voltaic cells (Solar cells)
These are the devices designed for use to convert the available sunlight into electrical
energy. This type of conversion does not involve any chemical reactions or moving parts in the
device. Primarily development of the concept came into light, way back in 1839.
French physicist. AC. Becquerrd, while working with electrodes in electrolytic
medium, observed development of voltage when electrode faced light. This effect was named as
photovoltaic effect.
Photovoltaic effect – Explaination
Sunlight is composed of tiny energy packets known as "photons". When sunlight falls
on solar cells, the photons with high frequency get readily absorbed. The light energy present
with photon is transferred to the semiconductor (eg. Silicon atom) particularly to electron in the
atom.
If electron receives sufficient energy, it escapes from its normal position, causing a
hole (i.e. an empty dot/spot where electron would be). This phenomenon proceeds causing one
hole with one photon, as it can strike only one electron. Since both electron/hole are mobile, they
are capable to carry current, which is nothing but "photo voltaic effect".
Working of PV cells / solar cell
The three layers present in PV cell work simultaneously for absorption of sunlight,
photovoltaic effect to occur, and conversion of heat into electrical energy as explained below.
The unique characteristics of semiconductor to act as good conductors when supplied with light
or heat and otherwise act as insulators at low temperature is been used effectively in solar cells.
The top junction layer is N-type made up using electron deficit material and lower or
back unction layer is P-type. The electropositive metals possessing only one valence electron are
used to form lower layer because they can lose electron easily leaving behind hole.
When sun light falls on the absorbing surface, the photons are absorbed and electrons
from lower layer are replaced (freed) to form hole. The free electrons move towards upper (top)
layer w-here it can be accepted because of electron deficit material.
This process continues involving flow of electrons to holes in the PV cell creating a
potential difference, at the P-N junction. Hence, current is generated at junction. The electric
field is thus created at junction.
Advantages of PV cells
(1) Clean technology.
(2) Can be used nearly for 20 years as there is no movement in cell;
Hence no wear.
(3) Maintenance minimal.
(4) Environment pollution issues do not arise.
(5) Can be used for domestic purposes, in industries automobiles etc.
Recent advances in PV cells
(1) The use of nanoparticles to improve efficiency.
(2) The use of cadmium telluride to reduce cost to PV cells.
(3) The organic solar cells (using polymers) and thin layer PV cells can be
manufactured more easily at low cost of materials

CHAPTER 5 : Phase Rule and Steels
 Give the demerits of phase rule.
Ans. : Demerits of Phase Rule
1.Phase rule can be applied for systems in equilibrium only.
2.It is not of much help in case of systems which attain the equilibrium state very slowly.
3.It applies only to a single equilibrium state. It does not indicate the other possible equilibria in the system.
4.Phase rule considers only the number of phases but not their quantities. Even a minute quantity of the phase,
when present, accounts towards the number of phases. Hence, care has to be taken in deciding the number of
phases existing in the equilibrium state.
5.All the phases of the system must be present under the same conditions of temperature, pressure and
gravitational forces.
6.The solid, liquid phases should not be so finely sub-divided as to bring about deviation from their normal
values of vapour pressure.
 State and explain phase rule. Discuss the application of phase rule to one component water system.
(7 Marks)
Ans. : Gibb's Phase rule may be stated as, "provided equilibrium between any number of phases is not
influenced by gravitational, electric or magnetic forces or by surface action, but only by temperature, pressure
and concentration, then the number of degrees of freedom (F) of the system is related to the number of
components (C) and phases (P) by; the phase rule equation.
F = C – P + 2
for any system at equilibrium at definite temperature and pressure." This rule does not have an exception, if
applied properly b:y maintaining the variables at a fixed levels.
Water System
The water system under normal condition is of three phases and one component system. The system
involved three phases are solid - ice, liquid - water, and gas - water vapour. All these phases can be represented
by one chemical entity H20, hence it is one component system.
Let us apply the phase rule to one component, i.e. water system. Substitute the value of component (C) = 1, in
the phase rule equation, then the equation is
F = C – P + 2
F = 1 – P + 2
F = 3 – P
From the above value of degree of freedom (F), we can say that, the degree of freedom (F) depends on
the number of phases present at the equilibrium.
Therefore, the following three different cases are possible, (Explained with the help of phase diagram,
refer Fig.).
Hence when,
P = 1, then F = 2 …… system is Bivariant

P = 2, then F = 1 …… system is Monovariant
P = 3, then F = 0 …… system is zero variant
From the above equation it is clear that, for arty one component system, the maximum number of
degree of freedom is two and most convenient variables are pressure and temperature. In the above phase
diagram of water system following salient features are observed:
1. The curves OA, OB and OC.
2. The areas AOC, AOB and BOC. 3.
3. The triple point '0' and
4. The metastable curve. (OA/
)
1. The curves OA, OB and OC
These three curves meet at the point '0' (called as tripple point) and divide the diagram in to three areas.
Therefore, these three curves ar1 known as boundary lines.
Curve OA (Vapour Pressure Curve)
The curve OA terminates at A, the critical point 218 atm. and 3740
temperature. It represents the vapour
pressure of liquid water at different temperatures. The two phases water and water vapour coexist in equilibrium
along this curve. Here, are two phases (P = 2) and one component (C = 1), therefore
F = 1 – 2 + 2 = 1
Hence, system is monovariant or univariant or having one degree of freedom. When the vapour pressure
is equal to one atmosphere, the corresponding temperature C as shown in figure is the boiling point of water, i.e.
100 C
Curve OB (Sublimation curve)
The curve OB terminates at B, the absolute zero, Le. - 2730
temperature. It shows the vapour pressure of
solid ice at different temperature
The two phases solid-ice and water-vapour coexist in equilibrium along this curve. Therefore, degree of
freedom for this system is also one and system is monovarient.
Curve OC (Fusion curve)
The curve OC terminates at C, the critical pressure. The two phases solid-ice and liquid-water coexist in
equilibrium.
This curve indicates that the melting point of ice decreases with increase of pressure.
The one atmosphere (1.0 atm.) line meets the fusion (freezing/melting) curve at O°C which is the normal
melting point of ice. Again, along the curve OC, there are two phases in equilibrium and system is of one
component.
Therefore, the system is monovarient.
From the above discussion, we can say that, along the curves OA, OB and OC there are two phases in
equilibrium and one component. Therefore,
F = C – P + 2
F = 1 – 2 + 2
F = 1
Hence, each two phases system has one degree of freedom, i.e. system is univarient or monovarient.
2. The areas AOC, AOB and BOC
The regions or areas between the curves show the conditions of temperature and pressure under which a
single phase, i.e. ice, water or water vapour is capable of stable existence. Thus
1. Area AOC represents conditions for liquid phase, i.e. water.
2. Area AOB represents conditions for gaseous phase, i.e. water vapour.
3. Area BOC represents conditions for solid phase, i.e. ice.
In all the three areas, there being 'one phase' and 'one component'.
Therefore,
F = C – P + 2
F = 1 – 1 + 2
F = 2
Hence, each system has two degree of freedom, i.e. system is bivarient or divarient.
3. Triple point
All the three curves, OA, OB and OC meet at the point 0 called as tripple point, where all the three
phases solid, liquid and vapour are simultaneously in equilibrium.
This triple point occurs at O.0075°C and 4.58 mm Hg pressure. Since, there are three phases and one
component, therefore

F = C – P + 2
F = 1 – 3 + 2
F = 0
The system at tripple point is zero variant or nonvariant. Thus, neither pressure nor temperature can be
altered.
Even slightly changed three phases would not exist if one of the phase disappears.
4. Metastable curve (curve OA’)
This curve is also known as supercooling (water/vapour) curve. This is the extension of curve OA, i.e.
vapour pressure curve. That is water can be supercooled by eliminating solid particles carefully which includes
crystallization.
The supercooled water system is unstable, i.e. metastable. It at once reverts to the stable system ice or
vapour on the slightest disturbance.
The metastable vapour pressure of super cooled water is higher than vapour pressure of ice.
 What are alloys steels?
What are the effects of following alloying elements on alloy steels :
(i) Nickel
(ii) Chromium
(iii) Cobalt
(iv) Tungsten
Ans. : Metals possess many useful properties, such as high malleability, ductility, luster, good electrical
conductivity being a few to mention. But, in nature metals are not available in pure state.
When metals are extracted from their natural sources - i.e. minerals or ores, some impurities are
carried along with the pure metals.
Hence, to get pure metal, further purification has to be done by various different methods. But after all
this processing, the pure metal obtained from its ore, loses some vital characteristics and becomes practically
useless for engineering purposes.
Some of such characteristics are, its tensile strength, corrosion resistance and hardness.
The pure metals are very soft, highly chemically reactive, highly malleable and ductile. Thus changes
in these vital properties, reduce shock and wear resistance of metals. The high chemical reactivity makes pure
metal susceptible to corrosion.
The properties of pure metals can be improved by alloying the pure metal with another suitable
meta/non-metal, e.g. iron in pure state can be alloyed to get steel, which shows the desired properties such as
hardness, toughness, high corrosion resistance etc. Here, steel is an alloy of iron with carbon (non-metal),
chromium/manganese (metals) etc.
An alloy is a solid mixture of two or more metals or non-metals. Alloy must have necessarily,
(i) at least one metal (base metal)
(ii) at least one additional metal or non-metal.
Element Special effects
ChromiumEnhance hardenability, corrosion and oxidation resistance, increase high temperature strength. In
high carbon steels, it increases abrasion resistance.
Cobalt Contributes to hardness of steel.
Nickel Along with other elements, renders moderate to high hardenability ; enhance strength of
unhardened steels by solid solution effect ; enhances toughness in pearlitic – ferritic steels.
Tungsten It helps to form hard and abrasion resisting carbide film in tool steels.
Imparts high temperature hardness in tempered steels.
It enhances creep strength in some high temperature steels.
 What is triple point in phase diagram? Explain it with reference to one component water system phase
diagram.

All the three curves, OA, OB and OC meet at the point 0 called as tripple point, where all the three
phases solid, liquid and vapour are simultaneously in equilibrium. This triple point occurs at 0.0075°C and
4.58 mm Hg pressure. Since, there are three phases and one component, therefore
F = C – P + 2
F = 1 – 3 + 2
F = 0
The system at tripple point is zero variant or nonvariant. Thus, neither pressure nor temperature can
be altered. Even slightly changed three phases would not exist if one of the phase disappears.
 Explain any two of the following terms :
1. Phase
2. Components
3. Degrees of freedom
Ans. :
(1) Phase
A phase is defined as any homogeneous, physically distinct and mechanically separable portion of a
system, which is separated from other such parts of the system by definite boundary surfaces.
Examples
1. In water. system, at freezing point of water, an equilibrium exists where ice, water and water vapours
are the three phases, each of which is physically distinct and homogeneous, and with definite boundaries
between ice, water and water vapours, as,
2. All gases mix freely to form homogeneous mixtures. Therefore, any mixture of gases, say and and
forms one phase only.
3. Two completely miscible liquids yield an uniform solution. Thus, a solution of alcohol and water is a one
phase system.
(2) Components
Definition
The term component is defined as, "the smallest number of independently variable constituents
taking part in the state of equilibrium by means of which the composition of each phase can be expressed
directly or in the form of chemical equation".
Examples
1. In water system, we have three phases, i.e. ice (Solid), water (Liquid) and water vapour (Gaseous) in
equilibrium. Each of these phases are different physical forms of the same chemical substance, i.e. H20. Hence,
system is regarded one component system.
2. In sulphur system, there are four phases, Le. rhombic sulphur, monoclinic sulphur, liquid sulphur and sulphur

vapour. The composition of all four phases can be expressed by one chemical individual sulphur (S). Hence,
sulphur system is regarded as one component system.
3. When calcium carbonate is heated in a closed vessel, the following reaction takes place.
Degree of Freedom (Variance)
Definition
Term degree of freedom is defined as, "the minimum number of independently variable factors such as
temperature, pressure and composition of the phases which must be arbitrarily specified in order to represent
perfectly the condition of a system".
Examples
In case of water system :
(a) If all' the three phases are in equilibrium, then no condition need to be specified because the three phases can
be in equilibrium only at particular temperature and pressure,
The system is no degree of freedom or invariant or zero variant or non-variant.
(b) If condition like temperature or pressure in altered, three phases will not remain in equilibrium and one of the
phase disappears.
For the following system :
We must state either the temperature or pressure to define it completely. Hence, the degree
of freedom is one or system univariant. ,
(c) For a system consisting of water in vapour phase only we must state the values of both, the temperature and
pressure in order to 'describe the system completely. Hence, the system has two degree of freedom or system is
bivariant.
 State and explain condensed phase rule. (3 Marks)
Ans. : Condensed or Reduced Phase Rule
When a single phase is present in a two component system, then the degree of freedom (F) is represented
by following equations;
F = C – P + 2
F = 2 – 1 + 2
F = 3
From the values of F (F = 3) we can say that, three variables must be specified in order to describe the
condition of phase, i.e. in addition to temperature and pressure the concentration of one of the component has to be
given.
 What are plain carbon steels? How can they be classified on the basis of carbon contents?
(3 Marks)
Ans. :
The alloys of iron with other metal (s) or/and non-metal are known as ferrous alloys. These are commonly
known as alloy steels. The metal iron generally forms alloys by mixing with carbon, and any other element (metal)
such as either nickel alone or nickel and chromium both. Based on this, the alloy of iron and carbon (i.e. steels -
widely known as plain carbon steels) are either,
(a) Three components i.e. (Fe, C, Ni)
or (b) Four components i.e. (Fe, C, Ni, Cr)
Since these 'steels essentially contain iron and carbon, are known as plain carbon steels. The percentage of
carbon in steels ranges from 0.008% to 2%. The plain carbon steels are further classified/named on the basis of its
carbon content as,

CHAPTER – 6 Nanomaterials
 Explain the structure, properties and uses of fullerene.
The fullerenes can be considered, after graphite and diamond, to be the third well-defined
allotrope of carbon. Fullerenes were first isolated in 1990, in considerable quantity.
The molecule was named after R. Buckminster Fuller, the inventor of geodesic domes, which '
conform to the same underlying structural formula. A hollow, pure carbon molecule in which the atoms lie
at the vertices of a polyhedron with 12 pentagonal faces and any number of hexagonal faces.
(When graphite was vaporised with a short-pulse, high-power laser) it turned into Fullerence - C60•
But this was not a practical method for making large quantities.
Each carbon is bound to three other carbons in a pseudo-spherical arrangement consisting of
alternating pentagonal and hexagonal rings, in the manner of a soccer ball. Hence its nickname, buckyball.
Every carbon is equivalent. NMR spectrum of C60 reveals a single line.
Buchminster fullerene is a beautiful thing it was found as a byproduct of soot formation.
Scrape the inside of the chimney and you will get few buckyballs on the finger.
Properties and applications
Fullerences are spheroidal organic molecules. Following are the physical and chemical properties of
fullerences,
1. Fullerene and its derivatives show superconductivity and ferro-magnetism.
2. The fullerenes are used in synthetic, pharmaceutical, and industrial applications, as
inhibitor of the HIV protease, to make new drugs or proteins.
3. fullerene are used in cosmetics preparation applicable in halting the process of aging.
4. The other type of fullerene C80 can act as a very good MRI contrast agent.
5. They can be useful in light emitting diodes (LED), molecular electronics and computing, as lubricants,
rocket fuel etc.
6. Fullerene C50, shows odd magnetic and electronic properties due to its shape being intermediate between a
sphere and a disk.
 What are (i) SWCNT and (ii) MWCNT ? describe the production of SWCNT by LASER method.
(6 marks)
In 1996 CNTs were first synthesized using a dual-pulsed laser and achieved yields of >70 wt%
purity. In this method the samples were prepared by laser vaporization of graphite rods with a 1 : 1 catalyst
mixture of Cobalt and Nickel at 1200°C in flowing argon, followed by heat treatment in a vacuum at
1OOO°C to get the Coo and other fullerenes.
The use of two successive laser pulses minimizes the amount of carbon deposited as soot. The
second laser pulse breaks up the larger particles ablated by the first one, and feeds them into the growing
nanotube structure. The material produced by this method appears as a mat of ''ropes", 10-20nm in
diameter and up to 100pm or more in length.
Each rope is found to consist primarily of a bundle of single walled nanotubes, aligned along ~
common axis. By varying the temperature, the catalyst
composition, and other process I,parameters, the average nanotube
diameter and size distribution can be varied. Arc-discharge and
laser vaporization are currently the principal methods for obtaining
small quantities of high quality CNTs.

 Write short note on, any two the following :
(i) Nanocones (ii) Haeckelites
(i) Nanocones
Carbon nanocones, were discovered in 1994 which are the most simple example of the
nanostructured carbon. They are made, of the hexagonal plane with a different number of pentagonai
defects, more precisely, from one to five.
Each cut, or the pentagonal disclination, has the angle 2 /6. The fivefold (or positive
disclination) could be stable, but the most stable configuration for more than one defect is the
configuration, where they are separated by hexagons.
The nanocones are produced by
1. Carbon condensation on a graphite substrate
2. Pyrolysis of heavy oil.
3. Laser ablation of graphite targets.
In laser ablation, graphite surface is heated with intensive short laser pulse. The graphite
evaporates some number of atoms from the graphene sheet, and other atoms rearrange into the conical
surface as shown above. The growth of nanocones is yet under study.
(ii) Haeckelites
The presence of defects such as pentagons and heptagons in fullerenes modifies the electronic
properties.

A new hypothetical type of grapheme sheet, which admits pentagons, heptagons and hexagons, has been
proposed, noting that the number of heptagons should be the same in order to compensate for the negative curvature
of the heptagons and the positive curvature of the pentagons
These arrangements are now called 'Haeckelites' in honour of Ernst Haeckel, a German zoologist
who produced a beautiful drawing of radiolaria (micro-skeleta of zoo-plankton), in which heptagonal,
hexagonal and pentagonal rings were observed.
Properties
They show metallic behaviour. Thus, it is possible to roll up Haeckelite sheets to form nanotubes,
which will be conductors, independent of the diameter and chirality. Another property of Haeckelite tubes
retain stiffness of classical CNTs, composed of only hexagons; (the Young's modulus of Haeekelite tubes
is around 1.0 TPa.) In addition, Haeckelites also exhibit local rugosity due to the local curvature
introduced by the presence of heptagons and pentagons.

 What are carbon-nanotubes? Explain different types of carbon-nanotubes. (2 marks)
Carbon particles as graphene sheets are made into tubular forms called as Carbon nanotubes.
They have diameters of few nanometers and their lengths are up to several micrometers. They were
discovered in 1991 by liJima. Carbon nanotubes have very important future applications.
Structural features
Each nanotube is made up of a hexagonal network of covalently bonded carbon atoms. Carbon nanotubes
are of two types:
(i) single-walled
(ii) multi-walled.
A single-walled carbon nanotube (SWNT) consists of a single graphene cylinder whereas a
multi-walled carbon nanotube (MWNT) consists of several graphene cylinders which are arranged in
concentric form. Due to such structures, these CNTS show electronic, mechanical, optical and chemical
characteristics, thermal conductivity, density, and lattice structure. which make them highly useful for
many application. The intrinsic properties of CNTS depend on the diameter
 Explain the use of nano materials in the field of any two of the following :
(i) Medicine
(ii) Electronics
(iii) catalysis (6 marks)
(i) Medicine
Nanomaterials are of the size 1 x 10-9
m. Hence they are comparable or even smaller than a
single cell 10 - 100 f.lm and virus 20 - 450 nm, protein 5 - 50 nm. Thus the materials can freely move
through tissues, they can also bind to a biological system. Endothelian layers of fast growing tumour
tissues are porous thus these nanoparticles can pass through them bringing out a specialised effect as a
medicine. Drug delivery is done through self assemblies like phospholipids or through block polymers.
The drugs molecules can be interrelated in lipohilic wall which acts like a cell membrane.
Liposome protects the drug from being assimilated during digestion or metabolised in certain
environments. Hydrophobic character of the liposome dissolves drug and allows it to pass through blood,
brain unaffected. When it arrives at a specific targetted site the drug is released due to temperature or PH
at the site inflamed of the organ or the concentration at the site lyposomes have PH 4 - 5 and tumour
tissues also have PH 4 - 5. Thus lyposomes open up at PH 4 - 5 allowing the drug to be released.
Magnetic components like magnetite or are coated with and then with
biocompatible polymer. This polymer has attachment point for the attachment with toxic drugs or anti
bodies. A magnet is placed outside the body near the target site to capture the magnetic particles, flowing
in a circulatory system.
Similarly the action of cytostatic anticancer drugs is localised there by reducing side effects on
the patients body especially arthritis, dextrane coated with iron oxides are used and are extracted via
liver treatment.
(ii) Electronics
To increase the speed at which electric charges work, the distance between them needs to be
decreased. Thus number of transistors per unit area increases every year. But there is a limit for this
growth. A time at which the space to store one bit becomes about 4 nm, the things happen at quantum
level heat will be developed, neighbourings bits would interact.
At present atomic scale memory is possible. A bit is encoded by the pres/abs of -Si atom inside
5 x 4 = 20 atoms. Thus 19 atoms prevent or absorb the heat energy. Thus storage capacity of hard disks is increased.
Thin films of organic materials emitting light (OLED) are known. Thin film transistors TFT and thin film organic
photovoltaic cells are known.
The deposition at a reasonable cost is possible because of organo inorganic metallic
compounds which are normally the self assembeled, nanomaterials. They can form thin films by simple
techniques the spray, spin cooling vapour deposition, inkjet printing etc.
(a) Displays

1. The huge market for large area, high brightness, flat-panel displays, as used in television screens and
computer monitors, is driving the development of some nanomaterials.
2. Nanocrystalline zinc selenide, zinc sulphide, cadmium sulphide and lead telluride synthesized by sol-gel
techniques (a process for making ceramic and glass materials, involving the transition from a liquid 'sol' phase
to a solid 'gel' phase) are candidates for the next generation of light-emitting phosphors. CNTs are being
investigated for low voltage field-emission displays; their strength, sharpness, conductivity and inertness
make them potentially very efficient and long-lasting emitters.
(iii) Catalysis
In general, nanoparticles have a high surface area, and hence provide higher catalytic activity.
Nanotechnologies are enabling changes in the degree of control in the production of nanoparticles, and
the support structure on which they reside.
It is possible to synthesise metal nanoparticles in solution in the presence of a surfactant to
form highly ordered monodisperse films of the catalyst nanoparticles on a surface. This allows more
uniformity in the size and chemical structure of the catalyst, which in turn leads to greater catalytic
activity and the production of fewer byproducts. It may also be possible to engineer specific or
selective activity. These more active and durable catalysts could find early application in cleaning up
waste streams.
This will be particularly beneficial if it reduces the demand for platinum-group metals, whose
use in standard catalytic units is starting to emerge as a problem, given the limited availability of these
metals.

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