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1.a)
The mechanism of polymerization of alkenes involves free radicals. The mechanism consists of
three steps.
(i) Initiation step (ii) Propagation step and (iii) Termination step
(i) Initiation step: For polymerization to take place, a small amount of initiator is necessary.
Peroxides, oxygen, azo compounds etc are used as initiators. The initiator forms free radicals that
initiate the polymerization reaction. The free radical furnished by the initiator attacks the double
bond of a monomer forming monomer free radical, which leads to the second step propagation.
Generation of initiator free radical.
(C6H5COO)2 2 C6H5COO
2CO2 + 2C 6H5( R)
Vinyl chloride
(ii) Propagation step: the free radical formed in the above step attacks another monomer
molecule to form another free radical. This process continues resulting in the formation of long
chain.
R- CH2- C HCl + CH2= CHCl R- CH2- CHCl- CH2- C HCl
Vinyl chloride
Mn = Total weight,
Mn
niMi
ni
Molecular weight of each particle is multiplied by total weight of this species. These
factors are added for all the size species and divided by the sum of weights of all
individual sizes.
(Since W1 = n1m1)
n1 M1 + n2 M2 +-----
Mw
niMi2
niMi
Tg = -110 oC
Tg = 100 oC
Tg = -18oC
Nylon-66 has strong intermolecular forces than polypropylene because of the presence of polar
amide group.
3. Presence of branching and cross-linking
Increase in branching and cross-linking restrict the chain rotation and therefore Tg increases.
4. Presence of plasticizers
Plasticizers are low molecular weight compounds are added to plastics to increase their flexibility.
They weaken the intermolecular forces between the polymer chains and decrease Tg. For
example adding a small amount of plasticizers such as diisooctyl phthalate to PVC reduces its Tg
from 80oC to below room temperature.
(ii). Branched chain polymer: A branched chain polymer is composed of a main chain with
one or more substituent side chains or branches.
E.g. low density polyethene (LDPE)
(iii).Cross linked polymer: Monomeric units are linked together to constitute a three
dimensional network. They are hard, rigid, and brittle.
e. g. Bakelite, epoxy, rubber etc.
CH3
CH3
n
H2C
Bulk/Suspension
Polymerisation
H2C
COOCH3
COOCH3
Methymethacylate
C
n
PMMA(Plexi-glass)
Properties:
1. It is clear, colorless and transparent polymer like glass.
2. It has high softening point of about 130-140C.
3. It transmits 98% of the sunlight including ultravoilt.
Applications:
1. It is used for making Aircraft windows, TV screens, plastic signs, helmet visors,
2. It is mainly used for automotive application such as signal light, lenses, dials etc.
3. Its sheets are used for signs, glazing skylights and decorative purposes.
ii) Teflon
Preparation, properties and applications of
Polytetrafluroethylene (Teflon, PTFE)
Properties:
1. It is highly-crystalline solid
2. It is very tough and strong due to the presence of strong C
F bonds
iii) Polyurethanes
Polyurethanes:
Manufacture:
Polyurethanes have the characteristic urethane NHCOO- linkages in their repeat units. Such a
linkage is prepared by the reaction of di-isocyanate with glycol in presence of tertiary amine
(acts as catalyst).
N(
)N
HO
Di-isocyanate
NH
(R)
OH
Diol
) NH
(R)
polyurethane
Properties:
1. It exhibits excellent resistance to abrasion and solvents
2. It exhibits high tensile strength.
Advantages/Application:
1. It is used as foams, coatings, films, adhesives and elastomers.
2. Resilient polyurethane fibers are used for foundation garments and swim suits.
3. Rigid polyurethane foams are used as heat insulating materials.
4. It is used for making bristles, Textile fibres, thin sheets etc.
An elastomer is a linear polymer which exhibits elasticity and other rubber like
properties.
Silicone rubber:
Manufacture: It is prepared by the reaction between a dialkyl dichlorosilane and water. This
produces a hydroxyl intermediate, which condenses to form a polymer called silicone rubber.
Properties:
1. It is highly inert and resistant extreme environments and temperatures from -55 oC to 300oC.
Applications:
1. It is used for making gaskets, foot wear, sportswear, artificial heart valves, sealants, non-stick
cookware coatings etc.
Applications:
1. Epoxy resins are mainly used in surface-coating materials which give outstanding toughness
flexibility, adhesion and chemical resistance.
2. It can be used in both moulding and laminating techniques to prepare glass fibre-reinforced
articles with good mechanical strength, chemical resistance and electrical insulating properties.
3. It is used as skid resistant for highway surfacing.
4. To impart crease-resistance and shrinkage control on cotton and rayon fabrics.
5. It is used as stabilizers for vinyl resins.
Kevlar:
Manufacture:It is prepared by poly condensation between aromatic dichloride and aromatic
diamines.
Properties: Kevlar is exceptionally stronger; it has high heat stability and flexibility
Applications: It is used extensively in the aerospace and air craft industries. It is also used
for making tires, industrial belts, bullet proof vests, high strength cloths, car parts (such as tyres,
brakes, clutch lining) etc.
Applications:
1. It is used as electrode material for commercial rechargeable batteries.
2. As conductive tracks on printed circuit board.
3. As film membrane for gas separation.
4. It can be used to produce smart windows that absorb sunlight and control solar energy.
5. It is used to control electromagnetic radiation.
ii) Dissolved CO2: H2O +CO2 H2CO3 which has slow corrosive effects on the boiler material. CO 2 is also released
inside the boiler of water contains bicarbonates
Mg (HCO3)2 MgCO3 + H2O + CO2
H2CO3 is responsible for pitting corrosion.
iii) Acids from dissolved salts: water containing dissolved magnesium salts liberate acids on hydrolysis. MgCl 2 + 2 H2O
Mg (OH)2 + 2 HCl
The liberated acid reacts with boiler producing HCl again and again.
Fe + 2 HCl FeCl2 + H2
Fe Cl2 + 2 H2O Fe(OH)2 + HCl , Presence of even a small amount of MgCl 2 will cause corrosion of iron to a large
extent.
7b)Define COD. Explain method of determining COD
Chemical Oxygen Demand (COD): It is the amount of oxygen in milligrams required to oxidize organic and inorganic
compounds present in one dm3 of waste water using strong oxidizing agent K2Cr2O7.
Principle: COD determination is based on dichromate reflux method because of higher oxidizing ability of dichromate.
The organic matter gets oxidized completely by potassium dichromate (K2Cr2O7) with silver sulphate as catalyst in the
presence of concentrated H2SO4 to produce CO2 and H2O. The excess K2Cr2O7 is titrated with ferrous ammonium
sulphate [Fe (NH4)2(SO4)2]. The dichromate consumed gives the oxygen (O2) required for oxidation of the organic
matter. The chemical reactions involved in the method are:
2K2Cr2O7 + 8 H2SO4 2 K2 SO4 + 2Cr2(SO4)3 + 8 H2O + 3O2
C6H12O6 + 6O2 6CO2 + 6H2O
Cr2O72-+ 6Fe2+ + 14H+ 6Fe3+ 2Cr3+ + 7H2O
Procedure:
Back Titration: Pipette out 25 cm3 of the waste water sample & 10 cm 3 of standard potassium dichromate solution
(using pipette) into a conical flask. Add one test tube of 6N sulphuric acid (containing silver sulphate & mercuric
sulphate) with constant shaking. Contents of the conical flask are Reflux for about 30 minutes on a water bath. The
solution mixture is cooled to room temperature. Add 2-3 drops of ferroin indicator and titrate against standard Mohrs salt
solution until the color changes from bluish green to reddish brown. The titre valve is noted (say V 1 cm3)
Blank Titration:
Repeat the above procedure by only 10 cm 3 of standard potassium dichromate without waste water. The titre valve is
noted (say V2 cm3).
Calculation: Normality of FAS solution = N1
Amount of K2Cr2O7 reacted with organic matter in terms of FAS = (V2 V1) ml
Volume of water sample taken for titration
= 25 ml
= 8 mg of oxygen
= C mg/liter of Oxygen
8a)Define BOD. How does it differ from COD? Explain the method of determination of BOD of the
water sample.
Biochemical Oxygen Demand (BOD): It is defined as the amount of oxygen required in milligrams by the
microorganism to bring about oxidation of biological compounds present in 1 dm 3 waste water over a period of five days
at 20oC.
COD (Chemical Oxygen Demand) is the amount of oxygen required to degenerate all poution in a chemical way (by adding oxidising agents and
heating). In general with chemical destruction you can remove more polution than with the biological way.As BOD is only a measurement of
consumed oxygen by aquatic microorganisms to decompose or oxidize organic matter and COD refers the requirement of dissolved oxygen for the
oxidation of organic and inorganic constituents both. Hence COD must be greater than BOD
Principle: The Biochemical Oxygen Demand (BOD) test measures the oxygen utilized for the biochemical degradation of
organic matter and oxidation of inorganic materials during a specified incubation period. Temperature effects are held
constant by performing a test at fixed temperature. The methodology of BOD test is to compute a difference between
initial and final Do of the samples incubation. DO is estimate by iodometric titration.
Procedure:
A definite volume of sewage sample is diluted to known volume with water which contains nutrients (1ml of phosphate
buffer pH = 7.2 (K2HPO4, KH2PO4 , Na2HPO4 and NH4Cl), 1 ml of MgSO4,1 ml of CaCl2, and 1 ml of FeCl3 for bacterial
growth and sufficient free oxygen. Equal volumes of diluted sample are filled into two BOD bottles (D 1 and D5).
Blank titration: Do content of D1bottle is determined immediately. 2ml of MnSO 4, 3 ml of alkaline KI are added into the
D1 bottle and mix well (for about 10-15minutes) and allowed to stand for 2 minutes. 1ml of con H 2SO4 is then added and
shaken well to dissolve the ppt. A known volume of this solution is against standard sodium thiosulphate using starch as
indicator till the disappearance of blue color. The titre valve is noted (say V 1 ml)
Sample Titration: The D5 bottle is incubated for 5 days at 20 oC. After 5 days unconsumed DO is measured as described
N 1 x V1
V2
above. N sample (D1) =
N sample (D1) = NNa2S2O3 X Vna2S2O3
Vsample(D1)
Amount of Oxygen available in sample (D1 bottle)
Amount of Oxygen available in sample (D1 bottle) = N sample (D1 X 8000 mg of oxygen
Amount of Oxygen available in sample (D1 bottle) = D1 mg of oxygen
Principle: DO in water is determined by Winkers method. This method is based on the indirect iodometric
titration. Manganese sulphate reacts with alkaline solution to give manganese hydroxide. Manganese hydroxide
reacts with DO to give basic manganese hydroxide and precipitated. Precipitation is dissolved by addition of con
H2SO4 and nascent oxygen is liberated. Nascent oxygen oxides potassium iodide to iodine. The liberated iodine is
titrated against standard Na2S2O3 using starch as indicator.
Mn(OH)2 + K2SO4
MnSO4 + 2KOH
[MnO(OH)2] + H2SO4
I2 + H2O + K2SO4
2NaI + Na2S4O6
I2 + Na2S2O4
ROCEDURE:
Determination of Dissolved Oxygen: Pipette out 25 cm3 of the waste water sample into a 250 ml conical flask. Add 2ml
of MnSO4, 3 ml of alkaline KI and mix well (for about 10-15minutes) and allowed to stand for 2 minutes. 1ml of con
H2SO4 is then added and shaken well to dissolve the ppt. A known volume of this solution is against standard sodium
thiosulphate using starch as indicator till the disappearance of blue color. The titre valve is noted (say V 1 ml).
CALCULATION: Normality of Na2S2O3 solution
Volume of Na2S2O3 solution rundown
= V1 ml
= N1
= 25 ml
= 8 gms of oxygen
= D PPM of Oxygen
i) Anion- exchange resins (ROH-) are mainly styrene divenyl benzene co-polymers, which contains amino or quaternary
ammonium or quaternary phosphonium or tertiary sulphonim groups as an integral part of the resin matrix. On treatment
with dil NaOH solution become capable to exchange their hydroxyl ions with the anions in the water.
Process: The hard water is passed first through cation exchange column, which removes all the cations like Ca 2+, Mg2+ etc.
from it and equivalent amount of H+ ions are released to water.
2 RH+ + Ca2+ R2Ca2+ + 2H+
RH+ + Na+ RNa+ + H+
Then hard water is passed through anion exchange column, which removes all the anions like SO 42-, Cl- etc. from it and
equivalent amount of OH- ions are released to water.
R OH- + Cl- RCl- + OH-
2R OH- + SO42- R2 SO42- + 2 OHNow H+ and OH- ions are combined to produce water molecule.
H+ + OH- H2O
Water coming out from the exchanger is free from cations as well as anions and is known as deionized or demineralized
water.
The anions pass through the anion permeable membrane towards the anode. However, these ions do not pass through the
next membrane which is permeable only to cations. Similarly the cations moving in the other direction will pass through
the cation exchange membrane but not the next. These anions & cations collect in the alternate chambers; the water in
these is enriched with salt while that in the other compartments is desalinated. The enriched & desalinated waters are
withdrawn separately. The water containing less salt recycled further to reduce the salt content.
11)What are nano materials? how are they classified? Explain with examples.
Nano materials:
One nanometer is defined as one thousand-millionth of a meter (10 -9 m).
Size dependent properties of nano materials: 1. Surface area: physical and chemical properties of a material depend
on its surface area. Surface area is increased on moving from bulk to nano scale. Nanomaterials have a significant
proportion of atoms existing at surface. Properties like catalytic activity, gas adsorption and chemical reactivity depends
on surface area.
For example: Finely divided nickel acts as an effective catalyst in hydrogenation of oil than bulk Ni.
2. Electrical properties: The electronic bands in bulk material are continuous due to overlapping of orbitals of atoms.
But in the nano size materials, very few atoms or molecules are present so the electronic bands become discrete. Hence,
metals which are good conductors in bulk become semiconductors and insulators, at nano level.
3. Optical properties: The nanoparticles of different size, can scatter radiation of different wavelength. For example.
Colors of few colloidal solutions. Nano particles of metals exhibit unique optical property called as surface Plasmon
resonance. When light falls on the surface of metal, electrons starts oscillating back and forth in a synchronized way in a
small space and the effect is called as Plasmon resonance.
11b)Describe the solgel method of synthesis.
1. Sol-gel process: Sol-gel process has been used in the synthesis of mono-dispersed nanoparticles of metal oxides and
temperature sensitive organic-inorganic hybrid materials. It consists of following steps: i) Preparation of sol ii)
Conversion of sol to gel iii) Aging of a gel iv) Removal of solvent v) Heat treatment
i) Preparation of sol: Sol is prepared by dispersing metal oxide or metal alkoxide (precursors) in a solvent.
ii) Conversion of sol to gel: Sol is then converted into a gel by hydrolysis and condensation of precursors. Hydrolysis and
condensation reactions are initiated by addition of an acid or a base iii) Aging of a gel catalyst.Gel on aging condenses to
nanoscale clusters of metal hydroxides. iv) Removal of solvent: The encapsulated liquid can be removed from gel by
evaporative drying. reactions are
v) Heat treatment: The sample is then calcined to obtain nanoparticles( 1 to 100 nm).
M(OC2H5)4 + x H2O M(OC2H5)4-x (OH)x + xC2 H5OH
temperature of the hot wall reactor results in the fertile production of nanosized particles of metals and ceramics instead of
thin films as in CVD (Chemical Vapour deposition) processing.