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- UNIVERSITY OF CALICUT i- I
UNIVERSITY OF CALICUT
(Abstract)
M.Sc Polymer Chemistry
i-
lrom 2OO9 admission
-
-
revised syllabus
-
implemented with effect
Orders issued.
GENERAL AND ACADEMIC BRANCH. I 'J' SECTION
Dated, Calicut University. P.O., 04.O2.2OO9.
No.GAI/J2 l8619l2Oo7.
1. Item no: 2 of tlrre minutes of the meeting of the Board of Studies in
ffead:
''
Polymer Chemistry held on O2-O7 -2OO8.
2. Item no. 2(xv) of the minutes of the meeting of the Faculty of Science
held on 29.08.2008.
3. Item no: II A (14) of the minutes of the meeting of the Academic
Council held on 07.10.2008.
4. Letter dated 23.01 .2OO9 from the Chairman, Board of Studies in
Polymer Chemistry.
ORDER
The Board of Studies in Polymer Chemistry vide paper read as l"t above,
approved the revised syllabus for M.Sc Polymer Chemistry to be implemented
with effect from 2OO9 admission.
The Faculty of Science vide paper read as 2nd above, endorsed the
decision of the Board of Studies & the Academic Council vide paper 3'd above,
approved the same.
Sanction has therefore been accorded to implement the revised
syllabus for M.sc Polymer Chemistry with effect from 2OO9 admission onwards.
The regulation, scheme of Examination & pattern of Question Paper remain the
same as that of existing sYllabus.
Orders are issued accordingly"Revised Syllabus is appended.
sd/DEPUTY REGISTRAR (G&A-rl
For RETGISTRAR.
To.
The Principals of all affiliated colleges offering
M.Sc Polymer Chemistry course.
Copyto:Controller of Examinations/Ex Section/DR(PG)
Tabulation Sec tion / Enquiry / Information Centre /
G&A-I'F' Section/G&A-II,III branches/ SF/DF/FC.
Forwarded/By Order
SECTION OFFICER.
A:\861 9-07(05.02.2009)Or(1 ).doc
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^"9
YL
LA B US- TH EO RY PAPE RS
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY. SEMESTER
PAPER
I.
THEORETICAL CHEMISTRY
I
I
(80 h)
uNrr I (11 h)
r) Mathematical Conceprs (6 h)
Co-ordinate systems: Cartesian, cylindrical polar and spherical polar coordinates and
their relationships. Complex numbers: definition, complex conjugate, absolute value
of a complex number, complex functions. Operator algebra: linear and nonlinear
operators, Hermitian operators, del and del-squared operators. Eigen function and
values of an operator, Eigen value equation, Eigen functions of commuting
"ig".,
operators. Well behaved functions, Normalized and Orthogonal functions.
li) Quantum Mechanics - A Historical Sketch (5 h)
AlalkUoay radiation and Planck's quantum postulate. Einstein's quantum theory of
ra{iation, Milliken's verification of Einstein's photoelectric equation, Wave-particle
duality of radiation. Compton effect. Louis de Broglie's matter waves, Electron
diffraction. Heisenberg's matrix mechanics (mention only), Uncertainty principle.
Schreodinger's wave mechanics, Deduction of Schrodinger equation from classical
wave equation.
uNrT rI (10 h)
l) Postulates of Qucintum Mechonics (4 h)
Detailed discussion of postulates: State function postulate. Operator postulate. Eigen
value postulate. Expectition value postulate. Postulate of time dependent Schrodinger
equation of motion, Conservative system and time-independent Schrodinger equation.
n) Quantum Mechanics of Translational Motion (6h)
Particle in a one-dimensional box, important features of the problem' Symmetry of
the wave functions. Particle in a three-dimensional box, Separation of variables,
Degeneracy, Symmetry breaking. Introduction to Tunneling'
UNIT
III
(12 h)
i) Quantum Mechanics of Vibrational Motion (5h)
Harmonic oscillator (complete treatment): Method of power series, Hermite equation
and Hermite polynomials, Recurssion formula, Rodrigue's formula, Wave functions
and energies. Important features of the problem. Harmonic oscillator and molecular
vibrations. Three-dimensional harmonic oscillator'
ii) Quantum Mechanics of Rotational Motion (7 h)
Rigid rotator (complete treatment): The wave equation in spherical polar coordinates.
planar rigid rotatoi (or Particle on a ring), The Phi-equation, Solution of the Phiequation, Handling of Imaginary wave fimctions, Wave func.tions in the real form,
Polar diagrams.
Non-planar rigid rotator (or particle on a sphere), Separation of variables, The Phiequation and the Theta-equation and their solutions, Legendre and Associated
Legendre equations, Legendre and Associated Legendre polynomials, Spherical
harmonics (Imaginary and real forms). Polar diagrams of spherical harmonics.
Spherical harmonics as eigen functions of angular momentum operators L2 and Lr,
Quantisation of angular momentum, Angular momentum quantum numbers, Space
quantisation.
uNrT rv (12 h)
Quantum Mechanics of Hydrogen-Like Atoms
Potential energy of hydrogen-like systems. The wave equation in spherical polar
coordinates, Separation of variables. The R, Theta and Phi equations and their
solutions, Laguerre and Associated Laguerre polynomials, Wave functions and
energies of hydrogen-like atoms, Orbitals. Radial functions and Radial distribution
functions and their plots, Angular functions (Spherical harmonics) and their plots,
Orbital diagrams.
Explanation of Hydrogen spectrum, Fine structure, The postulate of spin by
Uhlenbeck and Goudsmith, Dirac's Relativistic Schrodinger equation for hydrogen
atom and discovery of spin, Hydrogen wave functions including spin or Spin orbitals,
Construction of Spin orbitals from Orbitals and Spin functions.
uNrT v (12 h)
i) Quantum Mechanics of Mony- Electron Atoms and Approximation Methods (6 h)
Many-body problem, Approximation methods. Independent particle model,
Distribution of electrons in many electron atoms, Stoner's rule.
Variation method, Variation theorem with proof, Illustration of variation theorem
using a trial function [e.g., x (a-x)] for particle in a lD-box, Variation treatment for
the ground state of Helium atom, Effective nuclear charge.
Perturbation method, Time-independent perturbation method (non-degenerate case
only), Illustration by application to particle in a lD-box with slanted bottom,
Pertuibation treatment of the ground state of the helium atom.
Hartree-Fock Self-Consistent Field (HF-SCF) method. Slater's treatment of complex
atoms, Slater Orbitals, Slater's rules for calculating Slater orbitals.
il) Elecnon Spin in Many-Electron Atoms (3 h)
Construction of wave functions including spin for many electron atoms, Symmetric
and antisymmetric wave firnctions, Pauli's antisymmetry principle, Slater
determinants, Pauli's exclusion principle.
iii) Vector Model of Atoms and Spectroscopic
Terms
(3H)
Coupling of angular momenta, LS and JJ- couplings, LS coupling and Spectroscopic
term symbols for atoms. Electronic spectrum of hydrogen atom - the fine structure of
H.. line of the Balmer series.
2
NGAVI. Chemical Bonding, (t, n).^,^^.,ro Ernm _ onn
rtion. (2 h)
for a molecule, Born - oppenheimer approxlmz
i) Schrodingl.
"q"utiJ"
ii) Molecular Orbital (
MO theory of Hr*'
nt of homonuclear diatomic
MO
nucle mic molecules LiH' CO' NO'
molecules Lt2,B"z,Cz, N
HF.Correlationdiagrlrule.;troscopictermsymbolsfor
diatomic molecules'
iii) Valence Bond (VB) theorY (5 h)
VBtheoryofHz.VBtheoryofmo,"complexmolecules:BondinginBeHz,Hzo,
water'
g"oln"ttv, rrvutiaization' Examples: Methane'
NH3, orbital overlap. Molecular
VSEPR theory'
Ethylene, and Acetylene, Multiple bonds'
/f
(11 h)
Molecules (6 h)
Complex
, MO Theoryfor Moie
(Ethylene, Butadiene, Allylic anion),
HMo theory of linear conjugated hydrocarbons
of free\'ult"t' HMO theory of aromatic
Charge on an atom, bond order, Callulation
equation'
for the roots of the Huckel detenninantal
hydrocarbons (benzene). Formula
m"emonic device for cyclic polyenes'
UNIT Yll Chemical Bonding
FrosrHuckel
"i'cle
s(sh)
dipole-induced
ion dipole, dipole-dipole' ion-induced dipole'
irt"ru"ii'o"'- mathematical expressions - donor-acceptor
ones Potential'
References
l.
2.
3.
968'
F. L. Pilar, Eleme
rd University Press' 1983'
P. W. Atkins, Mo
n'' W'A' Benjamin Inc'' 1969'
M. W. Hanna, Quantum
.
,.
-rh
Inc., 2003.
Chemis*y,5,h -Edn., Pearson Education
;
i. *;";;ffirru*
TtLtv' Y-e"
s.D.A.M"a'iJ;:,'O:;;;;;;-Cn'*i'ov'universitvScienceBooks'1e83'
6.
[;"]iliir, ,rro.
7
'
cs' McGraw-Hill' 1935 (A
8.
good
9. R.L.
10.
ii.
R.
M.
K.
S. Pathania, Quantum
Publications, 1984'
0
-_ )
^t .-:^!-^. and
Chemistry
eaoatv,..?nrw
Spectroscopy
lutions), Vishal
I
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY_ SEMESTER
PAPER
II.
INORGANIC CHEMISTRY-
I
T
(80 h)
uNrr r (10 h)
Acid
base theories
- strength of acids and bases, solvent leveling effect, hard
and soft
acids and bases, super acids. Chemistry of non-aqueous
solvents- liquid NH3, SO2,
HzSoq and HF- Heterogeneous acid- base reactionssurface acidity,.soiid- and molten
acids in industrial processes.
uNrr rr (10 h)
Synthesis, structure, reactions and bonding
in
boron hydrides,
metalloboranes and borazines.
Synthesis, structure and applications of silicones.
Phosphorus- nitrogen, phosphorus- sulphur and sulphurnitrogen
compounds- synthesis, structure, bonding and applications.
carboranes,
ring and chain
Refercnces (For Units I and II)
I. D. Ir- Shriver, p. w. Atkins, c. H. Lang tbrd,Inorgunic Chemistry,ELns,
1990.
2' J' Il' Huheey, E'A' Keiter, R. L. Keitel,Irorgori chemistry,
principles, Struclure and
Reactivity, Pearson Education, I 990.
3' F' A' Cotton, G. Wilkinson, Advanced Inorganic Chemisrry, 5't' Edn., John
Wiley and
sons,1988.
uNrT rrr (12 h)
Crystalline solids, crystal systems, Bravais lattices,
crystal symmetry, symmetry elcments,
transitional and rotational transition symmetry, point
groups, space groups, indiies, Braggs
law, X- ray diffraction.
Close p
radius ratio, coordination number, lattice
energy,
z, AO2, AOl A2, 03, ABO3, AB2Oa type
crystal
alumino
of
polyhedra, structure
ons.
of
silicaies,
uNrT rv (10 h)
k- space, Brillouin zones, band structure. Fermi
states, metals, insulators, semiconductors,
types and structure
ctors.
b'and theory,
, Hume Rothery rules.
solid-liquid reactions, kinetics, thermal
and properties, preparative methods in solid
References (For Units
III and IV)
I' A' R' west, solid state chemistry and its Applications, John- Wiley,
chilchester,
2'
1984.
F' D' Bloss, crystallography and Crystal chemistry. Holt
Reinhart, winston, New
York, 1971.
3- A. F. wells,
structurar Inorganic chemistry,crarendon press,
oxford, r954.
4. A. K. Galway, Chemistry of Solids, Chapman- Hall, London, 1967.
-{ M. F. C. Ladd, Structure and Bonding in Solid State Chemistry, Elliz Harwood,
Chichester, 1979.
6. P. A. Cox, The Eleclronic Structure and Chemistry of Solids, Oxford University
Press.
7.
L.Y - Azaroff, Introduction to Solids. Mc Graw Hill,
1960.
UNIT Y. Nuclear Chemistry (10 h)
Radioactive decay and equilibrium- nuclear reactions- Q value, types of reactions- chemical
effects of nuclear transformation, y- recoil- effects of radiation on materials- fission and
fusion, fusion products and fusion yields- Radioactive techniques, tracer techniques- neutron
activation analysis- counting techniques such as G. M.-, ionization- and proportional counter.
References
1. J. B. Rajam, Atomic Physics, S. Chand and Co. pvt.Ltd.,lgl4.
2. J. W- T. Spinks, R. J. Woods, An Introduction to Radiation Chemistry, John Wiley
and Sons, 1964.
3. H. J. Anikar, Essentials of Nuclear Chemistry,4th Fdn., New Age Internation al, 1995.
4. S. Glasston, Source Book on Atomic Energgt,3'd Edn., East- West Press pvt. Ltd.,
1967.
5- Friedlander, J. W. Kennedy, Inlroduction lo Radiochemistry, John Wiley and Sons,
1981
6.
.
Friedlander, J. W. Kennedy, J. M. Miller, Nuclear and Radiochemislry,3'd Edn., John
Wiley and Sons, 1981.
uNrT vr (6 h)
Errors and treatment of analytical data, standard deviation, least square analysis,
statistical treatment of data sets, students tests, conhdence limit, Q test.
Theory of acid- base-, redox-, adsorption- and complexometric indicators, titrations in
non-aqueous solvents.
References
1. G. H. Jeffery, J. Bassett, J. Mendham, R. C. Denny, Vogel's Text book of Quantitotive
Chemical Analysis,5th Edn., ELBS, 1989.
2. Skoog, West, Holler, Fundomentals of Analytical Chemistry,8th Edn., Thomson and
Brooks,2004.
uNrT vrr (12 h)
Coordination chemistry formation and stability of complexes, chelate and macrocyclic
effect. The crystal field and ligand field theories, orbital splitting in octahedral,
tetrahedral and square planar fields, spectrochemical- and nephelauxetic series, JahnTeller effect. M.O. theory- composition of ligand group orbitats. M.O. diagrams of
complexes with and without n- bonding.
Standard reduction potentials and their diagrammatic representation. Ellingham
diagram, Latimer and Frost diagram. Pourbaix diagram.
rJNrT Vrrr (10 h)
Lanthanides and actinides- stable oxidation states, the lanthanide and actinide
contraction, the f orbitals, lanthanide chelates, separation of lanthanides and actinides,
transactinide elements.
References (For Units VII and VIID
l. D. F. Shriver, P. W. Atkins, C.H. Langford,Inorganic Chemistry, ELBS, 1990.
2. J. E. Huheey, E.A. Keiter, R. L. Keiter,lnorganic Chemistry, Principles, Structure
and Reactivity, Pdarson Education, 1990.
3. F. A. Cotton, G. Wilki nson, Advanced Inorganic Chemistry, 5'n Edn., John Wiley and
Sons, 1988.
6
*
Y'
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY _ SEMESTER
PAPER
III.
ORGANIC CHEMISTRY
I
I
(80 h)
uNrT r (12 h)
Delocalised chemical bonding, Electron Delocalization, Resonance and Aromaticity:
Qualitative application of Huckel MO theory and perturbation theory to systems
containing delocalized electrons. Delocalized electrons and Resonance, Resonance
hybrid and resonance energy. Criteria for Aromaticity and Antiaromaticity, MO
description of Aromaticity and Antiaromaticity. Homoaromaticity, Mobius twist and
Aromaticity. Aromaticity of Annuelens and heteroannulenes, Fullerines, and fused
ring systems. Stability of benzylic cations and radicals, Effect of delocalized
electrons on pKa.
Hydrogen Bonding:
Inter- and intramolecular hydrogen bonding. Range of the energy of hydrogen
bonding. Volatility, acidity, basicity and stability of hydrates of carbonyl compounds.
Stabilization of hydrates of glyoxal and chloral, and ninhydrin. Comparison of boiling
points of ethanol and dimethyl ether (two isomeric compounds). High volatility of onitrophenol and salicylaldehyde compared to their meto- and para- isomers. High acid
strength of maleic acid compared to fumaric acid.
uNrT rr (r0 h)
Basic Concepts in the Study oJ Organic Reaction Mechanisms
Application of Experimental criteria to mechanistic studies, Thennodynamic and
kinetic data, Curtius- Harnmet principles, Kinetic versus thermodynamic control.
Acidity constant, Ifammet acidity function. Reactive intermediates and their
characteization. Isotope effect (labeling experiments), stereochemical correlations.
Structure and reactivity, Transition state theory, Potential energy vs Reaction coordinate curve, Substituent effects (inductive, mesomeric, inductomeric, electomeric
and field effects) on reactivity. Qualitative study of substitution effects changing with
mechanism in SNI - SN2 reactions. Semiquantitative study of substituent effects on
the acidity of carboxylic acids. Quantitative correlation of substituent effects on
reactivity. Linear free energy relationships. Hammet and Taft equation for polar
effects and Taft's steric substituent constant for steric effect.
References (For Units I and II)
l.
J. March, Advanced Orgonic Chemistry,4h Edn., John Wiley and sons, 1992.
2.
T. H. Lowry, K. S. Richardson, Mechanism and Theory in Organic Chemistry, Harper
Collins, 1987.
3.
F. A. Carey, R.J. Sundberg, Advanced Organic Chemistry (Parts A & B),3'd Edn., Plenum
Press,1990.
4.
R. A. Y-
Jones, Physical and Mechanistic Organic Chemistry, Cambridge Universiqz
Press, 1979.
UNIT lll.Isomerism (10 h)
Dissymmetry' asymmetry and
chirality- simple and alternating axis
of symmetry- i:
conditions for optical u"ii,ity,Isotopic
,
ury-ir.
ric
variation
and
specilic
rotation o,the same compound in sign and
magnitual ,n0.. different conditions.
i"qu"n"e rule- R and s notati,or,r-ir'"r.ri" Relalive and
and acycric
:n"r:ff:nfiguration''
optical isomerism of compounds containing
one or more asymmetric carbon
atoms,
Enantiotopic, Homotopic, Diastereotopic
hyirogen atoms, prochirar centre.
optical isomerism in Biphenyls: Structu..
oi'uipr,.nyls in ,"ria,liqrid and vapour
states' structure of substituted
biphenyl.. N;;;.. oi substituenis
and their size in
relation to
lhe stability of optical iro.n.rr. R il s notation. Atropisomers. Restricted
biphenvls - Moiecular ou"...o*ai,r!.
chirarity due io folding of helioar
ff:',:lJ
conditions for optical activity in
allenes and spiro compoundsR and
33lTil
"l',il:H? J,'"ffi
I Hl ;T:Ll;;:-o",,ds-
nam
in
g-
S notation.
stereochemi stry
Geometrical isomerism E and
z notationof compounds with one and more double
bonds in acyclic systems' Methods
or a"i".mination of the contiguration
isomers in acyclic and cyclic
.yrtl-r, rnterconversion of geomerricarof
fl""#:""'l
Stereochemrstry of ardoximes
and ketoximes naming
determining configurations of
alcioximes and ketoximes.
-
isomerism
_ methods or.
References
l' J' March, Advanced organic Chemistry,4,h
Edn., John
wiley and sons, 1992.
2. Nasipuri, Stereochemiiiy of Organrc Co*pourir,
no
Edn.,
New Age international.
3' Kalsi' stereochemistry of drga,ni, co*pounds,wi
Eastern.
Suggested Reading
E' El-iel, S- H. wilen , stereoche tistry
of organic crmpounds, Johnwiley,
1994.
UNIT IY. Conformational Analysis (lg
h)
conformation and configuration.
Internal factors affecting the
conformation dipolar
interaction' bond oppofition st.ai.r,
uonJ *grl'^ strain, irt.a-ot".Jar bonding' Sawhorse and Newma,
hydrogen
projectioni Eclipsed, gauche
and
conformations. Conformations
staggered
or u"y"ti.
:
n$utane,
dihalide, glvcors, chlorohvdi irr,
,"ro'ut-)t-t^t*i"acids,
;;il#:
Ett"r-i---^-
;":*:::
acetardehyde and
of cyclohexane, conformations of firono_
and di_ substituted
cyclohexanes, conformation
of
decalins, and 2-halo"y"tot.**Jr.l.
group.
Conformation
*cilr*
ation
of
dl
dihalides (d/
and rate of reactions _ Sxl
and
andE2 eliminations of
s (cis and trans)
8
i
.,b,
-
(iii)
Menthyl and neomenthyl chlorides, and benzene hexachlorides.
Esterification of axial and equatorial alcohols and acids- their hydrolysis.
ORD and CD . Plane and single CE curves- uses. Axial haloketone rule and its
application. Octant rule- Determination of conformation and configuration of 3Methylcyclohexanone- ORD curves of cls- and trans- decalones.
References
l.
Nasipuri, Stereochemistry of Organic Compounds,Znd Edn., New Age International.
2. Eliel, Allinger, Anggal, Morrison, Conformational analysis, Wiley International.
3. I. L. Finar, Organic Chemistry, Vol. IL 5th Edn., ELBS, 1975.
UNIT Y. Reactions of Carbon-Heteromultiple Bonds (8h)
Addition to carbon-oxygen multiple bond: Addition of water, alcohols, amines and
hydrazine. Aldol, Claisen, Dieckmann, and Stobbe condensation. Darzen,
Knoevenagel, Wittig, Mannich and Prins reactions. MPV reduction and Oppenaur
oxidation. Cram's rule. Hydrolysis, alcoholysis and reduction of nitriles. Ritter
reaction and Thorpe condensation. Clemmenson and Wolf- Kishner reduction.
References
1.
J. March, Advanced Organic Chemislry,4'h Edn., John Wiley and sons, 1992.
2. Morrison, Boyd, Organic Chemistry, Prentice Hall.
3. F. A. Carey, R. J. Sundberg, Advancerl Organic Chemistry (Parts A & B),3'd Edn.,
Plenum Press, 1990.
uNrr vI
(8 h)
Electrophilic and Nucleophilic substitution in aromatic systems.
Friedel-Crafts alkylation and acylation. Orientation in monosubstituted benzenc.
Ortho-para ratio with reference to electronegativity and steric factors.
Nucleophilic aromatic substitution, Aromatic diazonium ions as synthetic
intermediates. Nucleophilic substitution as illustrated by the hydrolysis of 2,4dinitro-chlorobenzene. Amination of pyridine by sodamide (Chichibabin reaction).
Aryne mechanism. Examples, Detection of benzyne intermediate, orientation of
addition. Structure of benzyne.
References:
1. J. B. Hendrickson, D. J. Cram, G. S. Hammond, Organic Aemistry, McGraw
Intemational Book Company, 1981.
2. Morrison, Boyd, Organic Chemistry, Prentice Hall.
3. J. March, Advanced Organic Chemistry,4tn Edn., John Wiley and Sons, 1992.
Hill
UNIT Yll. Nucleophilic Substitution at Saturoted Carbon and Elimination Reactions
(8
h)
The four types of nucleophilic substitution reactions based on charges on the
nucleophile and leaving group. Nucelophilicity and size of nucleophile. Effect of
changing the basic nature of the leaving group. Effect of solvent polarity - solvent
effects on nucleophilic substitution of different charge types due to Ingold Y-value
and Dimroth parameter.
of Syl and Sp2 reactions. Reactions of epoxides and quaternary
ammonium compounds. Neighbouring group participation- participation of
Stereochemistry
carboxylate ion, halogen, hydroxyl group, acetoxy group, phenyl group and n bond.
Elimination at Bridgehead carbon
- Bredt's rule. c.ls elimination
rratrun - pyrotysts
pyrolysis ol
of esters
and Chugev reaction. ElcB mechanism.
References
1'
J. B. Hendrickson, D. J. cram, G.
s. Hammond, organic chemistry,McGraw
International Book Co rpany, l gg
l.
2.
emistry, prentice Ha
3.
4.
Edn.,
Organic
Che.mistry,4,h
plenum press,
1990.
Advanced
Hil
Wiley and Sons, 1992.
istry (parts I * il,l,o Edn.,
UNIT Yrrl' photochemicar and Erectrochemicar
synthesis. (6 h)
Basic conclPtl of.electroorganic
."actioor.'Ei..,..rr"rrical oxidation
and reduction
reactions' cathodic reduction
of organic r"r",i"ra groups like haro,
and electropolvmerisation rla"tio,,s. pr".t.o"r,"-icalnitro etc.
Ei::ff:i?:t',t#ion
sensors.
Industrial applications of organic
photochemistry.
References
1'
?
3
+".|
Fry' synthetic organic Electrtchemisrry,
Harper and Row publishers, New
R. O. Kan, Organic photochemislry,
McGraw Hill.
o'r Hetero,v,,ti,' itotochemistry,
fi;,,t, I*J,i;,1!*..]'ii:'^;::{ts
10
(o
Buchardt Ed),
UNIVERSITY OF CALICUT
M.SC.
PAPER
CHEMISTRY_ SEMESTER
IV.
II
THEORETICAL CHEMISTRY
II
(80 h)
UNIT l. Molecular Symmetry and Mathematical Groups (10 h)
Symmetry elements and symmetry operations in molecules, Complete set of
symmetry operations of a molecule, Point groups and their systematic identification.
Mathematical group, Finite and infinite group, Abelian and Cyclic groups. Group
multiplication table. Classes in a group, Similarity transformation.
Matrix algebra, Addition and multiplication of matrices, Inverse of a matrix, Square
matrix, Character of a matrix, Diagonal matrix, Direct product and direct sum of
square matrices, Block diagonalized matrix, Solving linear equations by the method
of matrices. Matrix representation of symmetry operations-
UNIT ll.
Theory of Molecular Symmetry 02h)
Repiesentation of groups, Basis for a representation, Representations using vectors,
atomic orbitals and Cartesian coordinates positioned on the atoms of molecule (H2O
as example) as the basis , Reducible and irreducible representations, Construction of
irreducible representation by reduction (qualitative demonstration only), Great
orthogonality theorem (GOT) (no derivation), Construction of irreducible
representation using GOT, Construction of character tables (Czv, Crv, Czn and C+v as
examples), Nomenclature of irreducible representations-Mulliken symbols, Symmetry
species. Derivation of reduction formula using GOT, Reduction of reducible
representations, (e.g., f.ur ) using the reduction formula, Direct sum and direct
product of irreducible representations. Connection between group theory and
quantum mechanics.
UNIT lll. Applications of Group Theory - 1(1 t h)
VaniSning and non-vanishing integrals. Transition moment integral and selection
rules. Overlap integrals and conditions for overlap.
i;
iD MO treatment of HzO, Classification atomic orbitals involved into
'
symmetry
(SALC),
Projection
combination
linear
adapted
Symmetry
species, Group orbitals,
operator, Construction of MOs, Electronic configuration of H2O, Symmetries of the
g.orrnd and excited states, Electronic transitions and'selection rules, Laporte selection
rule for centro symmetric molecules.
UNIT lY.Applications of Group Theory-Il(ll h)
i) Treatment hybridization in BFr and CHa, Inverse transformation and construction of
hybrid orbitals.
ii) Molecular vibrations, Symmetry species of normal modes of vibration,
Construction of fsarr. Normal coordinates and drawings of normal modes (e-g., H2O
and NH3), Selection rules for IR and Raman activities, Complementary character of
IR and Raman Spectra, Determination of IR active and Raman active modes of
molecules (e.g., H2O, NHt, CFIq, SFo).
UNIT
V
(12 h)
TheorY of SPectra
General
i)
Electromagnetic radiation and its different regions, lnteraction of matter with
radiation and its effqct on the energy of the molecule. Origin of molecular spectra,
l1
'l'heory of
the origin of rotational, vibrational
and electronic spectra.
speclrar lines, Dependence of intensity
on
pop rration, transition p
rransition moment integrar, serection
.rr".r. I-in: widths, Dopprer
Lifetime broadening
ii) Microwave Spectroscopy
Rotation spectra of diatomic and polyatomic
molecules, Rigid and non-rigid rotator
models' Asymmetric, symmetri"
and spt e.i.ut
iop*. Isotope
Stark effect, Nuclear and electron .pi, -irteractions. Jrr..t o, rotation spectra,
Rotational transitions and
selection
rules. Microwave spectrometer principles
&
Applications.
iii) Vi brational
Inslrumentation.
Spectros copy
vibrational spectra of diatomic and polyatomic
molecules, Harmonic oscillator
model' Anharmonicity, vibrational o*ritio".
and selectio, .rt"*- Morse potential,
Fundamentals, overtones, Hot bands,
comuinatitn bands, Difference bands.
uNrT vr (12 h)
i) vibration-rotation spectra of diatomic
and poryatomic morecures, p,e,R
branches.
IR and FTIR spectrophotometer - principles
a m.t.t r.r"ntation, Apprications.
ii) Raman Spectroscopy
Pure rotational' pure vibrational Raman
spectra, vibrational-rotational Raman
Seleclion rules, Mutual exclusion
principle.
l;ilffiX:trophotometer-
r'rinciptes
a
speotra,
Instrumentation, Laser Raman specrroscopy,
iii) Eleclronic Spectroscopy
,?ff::,rHfT]!:r'""r":,;.f.l}u*n
electronic ,d;;- of diatomic
law, Molar extinction coefficient, rntensity
or electronic
,rinciple, Ground and excited
L of polyatomic molecules,
cies_ Vibrational relaxation,
)rescence' Jablonski diagram.
dissociation spectra.
pplications.
Chromophores. The fate of
Externaic<jnr.rrior, Intemal c<
,Electronic spectra of conjugate<
UV-Visible rp."t opt otometer
uNrT Vrr (12 h)
vents used, Chemical
interaction, Coupling
constant, Factors influencing cc
molecules, Hindered rotatioi on
NMR spectrum, Karrs relalionship.,
Principles and instrumentation'
Multiple. NM\ sp;"dc"opy (brief
account). Applications of
spectroscopv to structure elucidation
of .i;p];;;;nic and inorganic molecules.
ilMfi
FT
;irffiT;"l$:T:]
ii)
ESR Spectroscopy
Theory and measurement techniques,
Hylrerfine interactions, Equivalent
and nonequivalent
protons, Kramer,s
EsRspectrometer_
principles and
t.o."p:
instrumentation.
Appiications
in structure elucidation of simple
-It.".rt"r.
12
,iii)
Moss Buuer speclr0scopy
{hc
Moss Bauer effect. Instrumentation. Ilypcrfine interactions, isomer shift, electric
c;uadruple and magnetio hyperfine interactions. Applioations.
iv) Mass Spectromelry
Basic principles, Instrumentation - Mass spectromeler, interpretation of mass spectra,
resolution, exact masses of nuclides, molecular ions, isotope ions. Fragmentation processes Mclafferty rearrangements, retro Diels - Alder fragmentation. Application in structure
olucidation and evaluation of heats of sublimation and ionization potential.
Refercnces
F. A. Cotto n, Chemical applications of Group Theory,2nd Edn., Wiley Eastern, l97l .
I.
2. Jaffe, Orchin, Symmetry in Chemistry, Wiley Eastern.
3. L. H. Hall, Group Theory and symmelry in Chemistry,McGraw Hill
4. R. McWeeny, Symmetry: An Introduction to Group Theory and ils Applications,
Pergamon Press, London, 1963.
5. P. H. Walton, Beginning Group Theory./br Chemislry, Oxford University Press Inc.,
New York, 1998.
6. A. W. Joshi, Elements o/ Group Theory Jbr Physicrsfs, New Age International
Publishers, 1997.
P. W. Atkins, I'hysical Chemistry,6'l' Edn., Oxfbrd [Jniversity Press, 1998.
7.
tl. Ir. Daniels, I{. A. Alberty, Physicul Chemi.;tr1'.5'l'l:cln.. Wiley Eastem, 1980.
9. D. A. Mo Quarrie, J. D. Simon, Physical Chemislry, A Molecular Approuch, University
Science Books, 1997.
10. K. J. Laidler, J. Il. Meiser, B. C. Sanctuary, Physicul Chemistry, Houghton Milllin
Company, New York, 2003.
I l. C. N. Banwell, Fundamenlals o/ Molecular Spectroscopy, Tata McGraw Hill, New
Delhi, 1994.
12. G. M. Barrow, Introduction to Molecular Speclroscopy,IvlcGraw Hlll,1962.
13. tl. H. Willard, L.L. Merritt, J. A. Dean, Inslrumenlul Methods of Analysis,4th Edn.,
14.
15.
Affiliated East-West Press Pvt. Ltd.,1965.
N. Sathyanarayana, Electronic Absorplion Speclroscopy and Related Techniques,
University Press, 2000.
R. S. Drago , Physical Methods in Inorganic ChemislrS,, Affiliated East-West Press Pvt.
Ltd.,7977.
l3
UNIVEITSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY _ SEMESTBR
PAPER
V.
PHYSICAL CIIEMISTRY
II
I
(80 h)
UNIT l. Thermodynamics 1(14 h)
i) Review of first and second laws. Third law of thermodynamics, need for the third
law, Nernst heat theorem, Apparent exceptions to third law, Applications of third law,
Determination of absolute entropies, Residual entropy.
Determination of relations connecting the thermodynamic partial derivatives by the
method of Jacobians (discussion to be confined to closed thermodynamic systemi).
ii) Thermodynamics of Solutions
Partial molar quantities, Chemical potential, Variation of Chemical Potential with
temperature and Pressure, Partial molar volume and its determination, Gibbs-Duhem
equation, Thermodynamics of ideal and real gases and gas mixtures. Fugacities of
gases and their determinations, Activity, activity coefficient, standard states of
substances (for solute and solvents). Duhem-Margules equation and its applications.
Thermodynamics of ideal solutions, Deductions of the laws of Raoult, ebullioscopy,
cryoscopy and osmolic pressure. Non-ideal solutions, Deviations from Raoult's law,
Excess functions - excess free energy, excess entropy, excess enthalpy and excess
volume.
UNIT ll. Thermodynamics 11(10 h)
Thermodynamics oJ' Irreversible Processes
Simple examples of irreversible processes. General theory of non-equilibrium
processes' Entropy production. The phenomenological relations. Onsager reciprocal
relations, Application to the theory of diffusion, thermal diffusion, thermoosmosis and
thermomolecular pressure difference, Electrokinetic effects. The Glansdorf-prigogine
equation.
References (For Units I & ID
1. S. Glasstone,ThermodynamicsJbr Chemists,East-West, 1973
2. Rajaram, Kuriokose, Thermodynamics, East-West, l9g6
3. R. P. Rastogi, R. R. Misra, An Introduction to Chemical Thermodynamics,New Age
. Intemational.
4. D- A. McQuarrie, J. D. Simon, Physical Chemistry, A Molecular Approach, University
Science Books, 1997.
5. K. J. Laidler, J. H. Meiser, B. C. Sanctuary, Physical Chemistry, Houghton Mifflin
Company, New York, 2003.
6.
Prigogine, An Introduction to Thermodynamics of lrueversible Processes, Interscience.
7.
B. G. Kyle, Chemical and Process Thermodynamics,2'd Edn., Prenlice Hall of India.
8.
G. K. Vemulapalli, Physical Chemistry, printice Hall of India.
UNIT
lll. Electrochemistry- I (Izh)
i) Debye-Huckel theory of electrolytic
conduction - Derivation of Debye-HuckelOnsager equation. Deviation from Debye-Huckel-Onsager equation and corrections.
Degree of dissociation and its determination. Conductance ratio. Debye-Falkenhagen
effect, Wein effect.
t4
ii) Activity and activity coefficients of electrolytes. Ionic strength, variation of
activity coefficient with concentration, Derivation of Debye-Huckel limiting law and
its various forms, Qualitative and quantitative tests of the Debye- Huckel limiting
law.
UNIT lY. Electrochemistry
-11 (10 h)
Polarization, overvoltage and polarography. Electrolytic polarization, dissolution and
deposition potentials, concentration polarization. Decomposition voltage and its
determination. Over voltage - hydrogen over voltage, oxygen overvoltage, metal
deposition over voltage and their determination. Theories of over voltage - Ionic
diffirsion as the slow process - Principles of polarography, dropping mercury
electrode, the half wave potential. Electrode kinetics.
References
l.
2.
3.
S. Glasstone, Introduction to Electrochemistry, East-West Press Pvt. Ltd., 1965
D. A. Mclnnes, The Principles of Electrochemistry, Dover Publications.
J. O. M. Bockris, A. K. N. Reddy, Modern Electrochemistry, Vol. I and II, Kluwer
Academic / Plenum Publishers, 2000.
UNIT Y. Surlace Chemistry and Colloids (10 h)
Langmuir's unimolecular theory of adsorption, Adsorption isotherms, BET equation,
derivation, determination of surface area of adsorbents, heat of adsorption and its
determination. Gibbs adsorption isotherm.
Colloids: Colloidal surfactants, classification cationic, ionic and ionogenic
surfactants. Micelles - causes of micellar formation. Micelle structure.
Determination critical micellar concentration stabilizing action of surfactants.
Practical importance of colloidal surfactants -'fannins and dyes.
UNIT YL Photochemistry (8h)
Radiative and non-radiative transitions - chemiluminescence photoluminescence,
cathodoluminescence, electroluminescence, bioluminescence, thermoluminescence,
fluorescence, theory of fluorescence, stokes antistokes and resonance fluorescence photosensitization - sensitised fluorescence - quenching of fluorescence. Theory of
quenching of fluorescence. Principles of utilization of solar energy- solar cells.
References
1.
2.
3.
4.
5.
6.
7.
F. Daniels, R. A. Alberty, Physical Chemistry, 5th Edn., Wiley Eastern, 1980.
S. Glasstone , Physical Chemistry, Mac
Millan and Company,1962.
G. Raj, H. Misra, Photochemistry,Goel Publishing House.
P. W. Atkins, Physical Chemistry, 6th Edn., Oxford University Pross, 1998.
C. H. Dupeg, R.L. Chapman, Molecular Reactions and Photochemistry, Prentice
Hall.
Cox, Kemp,Introductory Photochemistry, McGraw Hill.
P. Suppan, Chemistry and Light, RSC London.
1-5
UNIT Yll. Nuclear Chemistry (10
h)
Nuclear binding energy, semi empirical mass equation, stability rules, magic numbers,
nuclear models, shell, liquid drop, fermi gas, collective and optical models.
Nuclear reactions: Types, conservation, reaction cross section, compound nucleus
theory, specific nuclear reactions, photonuclear and thermonuclear reactions.
Nuclear fission- theory of fission - spontaneous and reduced fission - neutron capture
cross section and critical size, principle and working of nuclear power plants. Nuclear
fusion. Neutron activation analysis.
UNITVIII . Radiation Chemistry (6 h)
Radiation chemistry - interaction of radiation with matter - processes responsible for
energy loss, range and range energy relation. Methods of detection and measurement
of radiation. Physical and chemical radiation effects in solids. Radiation chemistry of
water and aqueous ferrous sulphate solution. Dosimetry. Principle and working of
GM counter and scintillation counters.
References
1.
23.
4.
5.
6.
F-riedlander, J. W. Kennedy, Introduclion to Radiochemistry,John Wiley and Sons,
1981
.
S. Glasstone, Source Book on Atomic Energt,3'd Edn., Affilialed East-West press
PYt. Ltd., 1967.
H. J. Arnikar, Essentials of Nucleur Chemistry. 4tl' Edn., New Age Intemational, New
Delhi, 1995.
J. B. Rajam, Alomic Physics, S. Chand and Co. pvt. Ltd., 1974.
Friedlander, J. w. Kennedy, J. M. Miller, Nuclear and Radiochemistry,3'd Edn.,
John Wiley and Sons, 1981.
J. w. T. Spinks, R. J. woods, An inlroduction to Radiation chemi.stry, John wiley
and Sons, 1964.
n
f
i
$
$i
t6
E
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY_ SEMESTER
PAPER
W.
ORGANIC CHEMISTRY
II
II
(80 h)
UNIT l. Pericyclic Reactions (10 h)
Definition and lypes of pericyclic reactions a)cycloaddition
and cycloreversion (b)
electrocyclic
ring crosure and ring opening c) sigmatropic rcarrangemcnr
.
Stereochemistry of pericyclic reactions ,n,i
th""o.y ol'molecula-r orbital sy,mnrctry.
Application ot' iheory o1' molecular orbital .y--.,.y
by the method of corelation
diagram
fbr
cycloaddition and electrocyciic reactiors
by both therrnal
and
photochemical paths.
Stereochemistrl' of pericyclic reactions- thermal
and pholochemical by method of'
transition state aromaticity.
Stereochemistry of pericyclic reactions by FMO.
Selection rules. Sommeret-Hauser, cope and
claisen rearrangements.
References
t.
T. H. Lowry, K. s. Richardson, Mechanism and rheory
in organic chemistry,Harper
Collins.
S. H. Pine, J. B. Hendrickson, D. J. cram, G. s. Hammond,
2.
organic Chemistry,
McGraw Hill International Book Company, l9gl.
3.
F' A. carey, R. J. Sundberg, Advoncid organic chemistry (parts
A & B),3d Edn.,
Plenum Press, 1990.
UNIT
Chemistry
\.Stability
of Free Radicals
(6h)
of free radicals. Formation and detection of free radicals.
structure and
stereochemical properties of radical intermediates
characteristics and reaction
mechanism involving radical intermediates. Free radical
substitution and
reactions' Rearrangement and fragmentation reactions.
Carbenes and nitrenes.
addition
References
l'
2.
3.
J' H' Lowry, K.
S. Richardson, Mechanism and Theory in Organic Chemistry,Harper
Collins.
J. March, Advanced
Chemistry,4'h Edn., John wiley and sons, 1992.
.org-anic
F. A. carey, R. J. sundberg,
Advanced organii chemistry go,rti i'i-as,'r,o ean.,
Plenum Press, 1990.
t7
UNIT IIl. Photochemistry (6h)
Fundamental Concepts, Molecular excitation, Jablonski diagram and the singlet
and
triplet states. Photosensitization.
rReactions involving the olefinic double bonds, reactions of carbonyl compounds
and
reactions of aromatic compounds. photoreduction. Di-pi-methane rearrangement.
Barton reaction and photo Fries rearrangement. Mechanism of photosynthesis,
photochemistry of dyes and pigments, photochemistry of vision.
References
1. R. O. Kan, Organic Photochemistry,McGraw Hill.
2. o. L. chapman, organic photochemistry vol. I & II, Marcel Decker.
3. F- A. Carey, R. J. Sundberg, Advanced Organic Chemistry (Parts A
Plenum Press, 1990.
& B),3'd Edn.,
UNIT IY. Molecular Reorrangements (Bh)
Rearrangement involving electron deficient carbon, nitrogen and oxygen
atoms,
Wagner-Meerwein, Dienone-phenol, Wolff, Hoffmann, Curtius, Lossen, Beckmann,
Schmidt and Baeyer-Villiger rearrangements.
Anionic rearrangements: Benzil-benzilic acid and Favorski rearrangements. Orten,
Claisen and Fries rearrangements.
References
1.
P. Sykes, A Guide Book to Mechanisms in Organic Chemistry, Orient Longmans,
2002.
2.
s- H. Pine, J. B. Hendrickson, D. J. cram, G. s. Hammond, organic Chemistry,
McGraw Hill International Book Company, l9gl.
J.
J. March, Advanced organic chemistry,4'h Edn., John wiley and
sons, 1992.
UNIT Y. Organic Spectroscopy (20 h)
Application of UV, IR, NMR, and MS in the structure elucidation of organic
compounds. Problem solving approach (Instrumentation not required).
UV: Characteristic absorption of organic compounds - Empirical rules for
calculating
absor-ption maxima of dienes and enones
sorptions of organic morecules - Arkanes, alkenes, arkynes,
rocarbons, alcohols, phenols, ethers, carbonyl compoundE
NMR: The chemical shift, Local diamagnetic shielding and magnetic equivalence.
Spin-spin coupling and coupling constants. Coupling-of protoris
to other nuclei Homotopic, enantiotopic and
sonance, Vicinal and geminal
chemical shifts. Correlation
coupled and noise- decoupled spectra.
MS: Determination of molecular mass. Molecular formula hom lsotope
ratio.
Fragmentation pattern in different classes of compounds. Modern
techniques of
ionization.
18
I
i . .Ref'crcnces
-+r.
Silverstein, G. C. Basslar, T. C. Morrill, Speclroscopic ldenldicatittn
Orgonic Compounds, John Wiley and Sons Inc', 1991.
W. Kemp, Organic Spectroscrtpy,3'u Edn., McMillan. 1991.
P. S. Kalsi, Spectroscopy of Organic Compounds, New Age International, 1998.
I{. M.
2.
3.
o.f
UNIT Yl. Organic Reaclions and Mechanisms (8h)
Robinson annulation, Birch reductions, hydroboration, Favorski reaction, Stork enamine
reaction, Michael addition, Sharpless asymmetric epoxidation, Hofmann- Loffler- Freytag
reaction, Shapiro reaction and Bayer- Villiger reaction.
References
l. F. A. Carey, R.J.Sundberg, Advanced Organic Chemistry (Parts A & B),3'd Edn.,
Plenum Press, 1990.
2. H. O. I{ouse, Principles of Organic Synthesis.
3. J. March, Advanced Organic Chemistry,4tn Edn., John Wiley and sons, 1992.
UNIT Yll. Heterocyclic Compounds
and Natural Product Chemistry (10 h)
Structure, synthesis and reactions of pyrazole, imidazole and thiazole. Synthesis of
uracil, thymine, cytosine, adenine, guanine, caffeine and pyrazine. Iliosynthesis of alkaloids,
terpenoids, steroids, carbohydrates and proteins.
Ref'erences
I
.
UNIT
I. l-. Finar, Organic Chemislry Vol. il,5th Edn., ELBS, 1975.
Ylll.
Synthetic Reagenls (12 h)
Uses of the following reagents in organic synthesis. Complex metal hydrides. Gilmans
reagent, lithium diisopropyl amide (LDA), DCC, 1,3-Dithiane (reactivity umpolung),
trimethylsilyl iodide, tri-n-butyl tin hydride, OsO4, DDQ, SeOz, Woodward and Prevost
hydroxylation, phasc transfer catalysts, crown ethers and Merrifield resin, Peterson's
synthesis. Wilkinson catalyst and Baker yeast.
References
1.
F. A. Carey, R.J.Sundberg, Advanced Organic Chemistry (Parls A & B),3'd Edn.,
2.
3.
Plenum Press, 1990.
H. O. Housq, Principles of Organic Synthesis
J. March, Advanced organic chemistry, 4th Edn., John wiley and sons, 1992.
19
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY_
SEMESTER
PAPER
UNIT I. Statisticol Mechanics_
f
VII.
PHYSICAL CHEIII$TRY
III
II
(80 h)
04 h)
i) Basic principles' permutations, probability
distribution of particres in energy
Microstates and macrostater
states.
r"""rrgr."ii"'rJ"
statistical
weight
factor
(g), Most
probable distribution- Boltzman
distribution law. The partition
function and its
relation to the thermodynamic
functions.
ii) The perfect Gas
Factorisation of the partition
function into translational, rotational,
vibrational and
electronic P,arts' The corresponding
contribuiions to the thermodynamic
.
properties.
heat capaciiy- temperature retation
r". r,ya."g"# ortho
#;#J"lous
ant) para
iii) The atomic crystal- Einstein's theory
of atomic
UNIT It. Statisticat Meihonics_ II (14
h)
crystars- Debye,s modification.
i) The imperfect gases- The virial expression
and the
belween the viriar coefficients
ancr lhe
ini.g.utr.
virial coefficients- relation
"irrt".
ii) i'he
ideal Fermi gas- Fermi- Dirac
distribution -law- Equation of state
of an ideal
Fermi gas- limiting forms of the
expression at (a) high temperatures
and row densities
(b) low temperature and high
densities. nppri"uiinn to electrons
in metals.
iii) The ideal Bose gas
ffi,,T,h
t;H:l
fj,T,::,'",
law
Apprication to Bose_ Einstein
condensation.
References
l'
G. S. Rush Brooke, ,statisticar
Mechanics, oxtbrd University press.
2. T. L. Hill, Introduction to
3.
4.
5'
K.H
o.K
F'
c.
um statisticar Mechanics,
Johr w,ey
y.
and Co.
and sons, 1963.
UNIT lII. Chemicat Kinerics_.l (12
h)
i) Theory of reaction ra
theory. Significance .
t theory and transition state
oretical calculation of the
ration. A comparative study
activation energy - potent
of collision and transition
olecular reactions.
ii) Kinetics of reactions involving reactive
atoms and free radicals. Rice
mechanism and
state approximation
- Herzferd
in the kinetics of organic gas phase
-steady
decompositions' Kinetlcs
of chain reactions - branching
chain and explosion limits.
20
-*'
rt^
rUNIT lY. Chemical Kinetics-
'
II
(14 h)
i) Catalysis - Theories of general and specific acid - base catalysis - enzymecatalysis
- Michaelis Menten equation - heterogeneous catalysis - theory and principles -
industrial applications.
ii)
Kinetics of reactions in solution - role of solvent in the kinetics of reactions cohesive energy density of solvent and its influence on rates - effect of specific
properties of solvent such as dielectric constant and dipole moment on rates of
reactions between ions, dipoles and neutral molecules. Salt effect, primary and
secondary salt effects: Fast reactions - study of the kinetics of fast reactions using
relaxation time - Flash photolysis.
References
l.
2.
3.
45.
6.
K. J. Laidler, Chemical kinetics, Vol. I and II, McGraw Hill.
A. A. Frost, R. J. Pearson, Kinetics and Mechanism,wiley Eastern.
F. Daniels, R. A. Alberty, physicar chemistry, 5th Edn., wiley Eastem, 19g0.
G. K. vemulapalli, Physical chemistry, printice Hall of India.
D. A. McQuarrie, J. D. Simon, Physical Chemistry, A Molecular Approach,University
Science Books, 1997.
K. J. Laidler, J. H. Meiser, B. C. Sanctuary, Physical Chemislry, Houghton Mifflin
Company, New York, 2003.
UNIT Y. Introduction to Computers in Chemistry (14 h)
Basic ideas of CPU, input and output devices, memory. Hardwares and softwares.
System softwares and application softwares.
Programming Languages: machine, assembly, high level languages. lnterpreter and
compiler. Flow charts and Algorithms. Introduction to BASIC languagi, BASIC
characters, Numeric constants and variables, String variables, Symbols of arithmetic
operations, Hierarchy of operations. BASIC Statements, (Jser defined functions.
-
Writing simple prograrnmes in BASIC: Factorial of a number, Method of least
squares, Determination of empirical formula of hydrocarbons, dipole moments of
disubstituted benzenes, delocalization energy of aromatic systems, molecular weight
of an organic compound, lattice energy of ionic crystal using Born-Lande equation,
solubility of sparingly soluble salts, half life & average life of a radio active elements.
Calculation of energies and wave functions of a partiele in a l-D box and plotting the
wave functions and probability densities using spread sheet (e.g., EXCEL),
Calculation of Hermite polynomials.
Introduction to C language, C characters, Constants and Variables, C statements. C
programming, Factorial of a number, Molecular weight of organic compounds.
Basic ideas on the use of Internet in Chemistry Education.
References
l. J. B. Norton,Introduction to BASIC, BPB publishers.
2. S. M. Venit, Programming in BASIC, Problem Solving with Structure and Style, Jaico
Publishing House, Bombay.
3. Madric, Donevan, Understanding Computers, McGraw Hill.
4. K. V. Raman, Computers in Chemistry, Tata McGraw Hill,l993.
5. K. B. wiberg, computer Programmingfor chemists, Benjamin Inc., Ny, 1965.
2t
6.
7.
8.
N. Subramaniam, programming in Busic,A.L.Wheeler
and Co.
t;"?lrrrZ
,"mputeis iy
,l::'_?"!
!.hemiytrt, John wiley and Sons, Ny, le8l.
Ramesh Kumari,
Computers and rheir
Apprications
in7*",Jrii"i,;;",'ril*
*
o"rt;i
S. P. Singh, Fundamentals of Computers.
?.
10. Bala Guruswamy, programming in BASIC.
I l. Yesharant Kanetkar, Let (Is C,BPB prblirh".r.
UNIT Yl- Introduction to computofionar
euantum chemisrry e2h)
Review of Hartree-Fock SCF method, Electronic
structure of molecules, The basis
sets' STos and GTos, Nomenclature of basis
sets. Semi-empirical and ab initio
methods. Cal
Programme, Specification of molecular
geometry usin
and b) Inte_rnal coordinates, The Z_matrix,
of
Z_matrices
Methanol), The structure of a Gaussi*
k[:,g;rJr, 'ro,
Formaldehyde, Ammonia,
References
1'
2'
3'
4'
D' A. McQuarrie, J. D- Simon, physicar chemistry,
A Morecurar Approach,
University Science Books, 1997.
I. N. Levin, euantum che:mistry,5h Edn., pearson
Education, Inc., 2000.
T.
Computationar chemistry,Iohnwiley and
Sons, Inc., I9g5.
F.
computationar chemistry, Jolnwiley and
Sons, 1999.
clark,
Jensen
22
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY_ SEMESTER
PAPER
WII.
INORGANIC CHEMISTRY
III
II
(80 h)
uNrT r (10 h)
Electronic spectra of complexes. Terms of dn configurations,
selection rules. Effect of
ligand field on RS terms. orgel diagram and its uses. Charge
transf'er transition,
spectra of lanthanides.
Magnetic properties of metal co
paramagnetism- the Curie and Curie
quenching of orbital magnetic mome
lanthanides, antiferro magnetic interact
uNrT rr (10 h)
Reaction mechanisms of metal complexes- classification, substitution
reactions in
octahedral complexes. A, D and I mechanisms, aquation
and base hydrolysis.
Substitutions in square planar complexes- trans effect, theories
and applications.
Redox reaction mechanism, inner and outer sphere mechanisms,
Marcus theory,
photochemical rcactions of metal complexes.
uNrT rrr (8 h)
Infrared spegtra o1- metal complexes. Changes in ligand vibrations
on coordinationmetal ligand vibrations. CD- and oRD spectra of metal complexes.
IISR spectra application to copper complexes, Mossbauer spectra - application to iron
complexes.
uNrT rv (10 h)
organometallic compounds- Classification and nomenclature, alkyls
and aryls of
main group metals, structural types, metal carbenes and carbines.
and bonding in metal carbonyls.
S1'nthesis, structure, reactions and bonding in metal complexes
of ethylene, allyl,
butadiene, acetylene.
l'he lS-electron rule, syntheses, structure
uNrT v (10 h)
_
Synthesis, structure, bonding and reactions of complexes of CaHa,
C5H5 (iron group),
C6tl6(chromiumgroup).
Fluxional Or ganome tal lic s
Metal-metal bond and metal clusters- structure and bonding in halide
clusters and
higher carbonyl clusters. Metal complexes of H2, Nz Oz and NO- structure
and
bonding.
uNrT vr (8 h)
Applications of organometallic compounds in organic synthesis and catalysisoxidative addition, reductive elimination and insertio, ..u.iionr. Carbonylation
by
Collman's reagent. Hydrogenation, hydroformylation and polym erization
of alkenes
using organometallic catalysts. Monsanto acetic acid process, Wacker process.
23
uNrT vrr (10 h)
Introduction to bioinorganic chemis
bulk and trace metal ions, coord
Metalloenzymes- cytochrome p450,
vitamin B12. Oxygen transport_ hem
metal ions- Ferritin, transferring.
Biological nitrogen fixation, chlorophyll- photosystem
I and II. platinum complexes
as anticancer drugs.
Referenccs
1' F' A'
2'
a
J.
4.
5.
Cotton, G. Wilkinson, C. A. Murillo, M. Bochm ann. Advanced
Inorganic
Chemistry, John Wiley & Sons, 1999.
J' E' Huheey, E' A Keiter, R. L. Keiter,Inorganic Chemistry, principles
Structure anrl
Reactivity, Pearson, 2001.
H. J. Emeleus, A. G. Sh^a^+, Modern Aspects of Inorgaryic
Chemistry.
P. P_owell, Principres of organometoilii chemistry,ino
Edr., ELBS, r9gg.
R. c. Mehrothraz, A. Singh, organomelailic Chemistry, A
Unified Approach, wiley
Eastern,
1991.
K. F. Purcell, J. C. Kotz,Inorganic Chemistry.
S. Ir. kettle, Coordination Compounds.
Sutton, Electronic Spec.tru oJ' (.'oordination Compounds.
6.
7.
8.
UNIT Ylll.Instrumental Methods of Analysis (14 h)
Electroanalytical techniques:
.voltametry,- cyclic voltametry, polarography,
amperometry, coulometry, conductometry,
spectrophotometry. i"t".mut analysis:
Principles, TG, DTA and DSC- their -appiications, polarimetrf
refiactometry,
chromatograply- column, paper, TLC., cas a"a HPLC.
Determination of Rrvalue.
Principles of3]9mic absorption speotroscopy (AAS) and atomic emission
spectroscopy (AES), solvent extraction and ion exchange
methods, light scattering
teehniques including nephelometry.
References
l2'
3'
4.
G. H. Jeffery, J. Bassett, J. Mendham, R. c. Denny, voge|s
Text book of
Quantitative Chemical Analysis, 5th Edn., ELBS, 19g9.
williard, Merrit, Dean Instumental, Methods in Chemistry.
Skoog, West and Holler, Fundamentals of Analytiiat
Thomson and Brooks, 2004.
R. S. Drago, physical Methods in Inorganic Chemistry.
24
Chemistry, gth Edn.,
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY_ SEMESTER
PAPER
IX.
III
POLYMER CHEMSITRY
(80 hours)
uNrr r (12 h)
Basic concepts of Polymer science, history, molecular weight and its distribution,
synthetic and natural polymers.
Classification as Plastics, rubbers, fibres, adhesives and coatings.
Plastics- thermoplastics and thermosets, commodity, engineering and speciality
plastics; Rubbers- general purpose and speciality rubbers, sources of monomers,
polymerisability, stereoohemistry, conformational analysis of polymers.
uNrT rr (8 h)
Synthesis of high polymers, reactants for step growth polymerisation, vinyl
monomers, step reaction (condensation) polymerization, mechanisms, kinctics and
statistics, gelation.
uNTr rrr (10 h)
Radical chain (addition) polymerization, mechanisms of vinyl polymerization:
initiation, propagation and termination. Kinetics of vinyl radical polymerization,
degree of polymerrzation and chain transfer determination of individual rate
c:onstants, effects of temperature and pressure on chain polymerization.
uNrT rv (10 h)
Ionic and coordination chain (addition) polymerization, cationic polymerizalion,
mechanisms, kinetics, anionic polymerization, mechanism, kinetics, coordination
polymerization, Ziegler- Natta catalysis, ring opening polymerization.
uNrT v (10 h)
-
Copolymerisation, kinetics, . copolymer equation, monomer reactivity ratios
evaluation, rate of copolymerisation, composition of -copolymers, mechanisms, ionic
copolymerisation, step reaction copolymerisation, block and graft copolymers.
uNrr vr
(10 h)
Polymerisation conditions, comparison of polymerization systems, polymerization in
homogeneous systems and heterogeneous systems, Smith-Ewart kinetics, solid phase
polymerisation, pol ym erization reactors.
uNrr vrr
(8 h)
Reaction of polymers, reaction with polyolefins, polyenes, aliphatic pendant groups,
aromatic pendant groups, cross-linking reactions, preparation of polymer derivatives.
25
uNrT vrrr (12 h)
Polymer degradation and stabilization: introduction, chemical degradation, physit*degradation, photodegradation, thermal degradation, aging, degradation by
microorganisms, biodegradable polymers- stabilisation, antioxidants.
References
1
.
F.
w . Billmeyar, Text Book of polymer
science, John wiley and Sons.
2.
R. B. Seymotx, Polymer Chemistry, Marcel Dekker.
3.
J. R. Fried, Polymer science
and Technologt,prentice Hall.
26
\
)
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY_ SEMESTER
PAPER
X.
III
POLYMER MATERIALS
(80 h)
uNrr r (lo h)
Natural polymers: Proteins- Synthesis of peptides (solution and SPPS), structure of
proteins, Nucleic acids- structure and synthesis in detail, lignins, cellulose, properties
and applications, source, rubber latex, processing, dry rubber, technically specified
and classified rubbers, modified forms of NR, reclaimed rubber, reclaiming processes.
uNrr rr (lo h)
Structure, preparation, preparation and applications of polyolefins: polyethylene,
LDPE, HDPE, LLDPE, chlorinated and chloro sulphonated polyethylene, ethylene
copolymers, polypropropylene, polypropylene copolymer, polyisobutylene, butyl
rubber etc.
uNrr rrr (12 h)
Vinyl polymers;
structure, preparation, properties and applications polystyrene,
styrene based copolymers SAN, ABS, high impact polystyrene polyvinyl chloride,
chlorinated PVC, vinyl chloride- vinyl acetate copolymer, poly(vinyl acetate) and its
derivatives poly (vinyl alcohol), fluoro polymers; PTFE, PCTFE, PVF and PVDF,
poly acrylics, PMMA, poly acrylonitrile, transformation into carbon fibre, poly
acrylic acid.
uNrr rv
(8 h)
Diene polymers; structure preparation, properties and applications, polybutadiene
rubber, styrene-butadiene rubber, oil extended SBR, thermoplastic elastomers from
styrene-butadiene copolymers, nitrile rubber, polyisoprene, polychloroprene.
uNIr v
(10 h)
Polyesters: structure, preparation, properties and applications of thermoplastic
polyesters, PET, PBT, thermoplastic polyester elastomers, polycarbonates, poly
acrylates, liquid crystal polyesters, thermosetting polyesters, unsaturated polyesters,
epoxy polymers.
uNrr vr
(10 h)
Polyamides and polyimide: structure, preparation, properties and applications, nylon
6, nylon 6,6 polyamide thermoplastic elastomers, aromatic polyamides, polyimides,
modified polyimides, phenolics, novolacs and resoles, aminoplastic: UF & MF.
uNrT Yrr (r0 h)
Silicon polymers; structure, preparation, properties and applications, silicon oils,
silicon elastomers, polyurethanes, structure, preparation, properties and applications,
thermoplastic polyurethane elastomers, polyurethane rigid and flexible foams.
27
uNrT Vrrr (10 h)
j^",,#-": jT"":,,r. resistant polymers,
il#*l
photoresistr'polv-"..i"n.r,+r";;,ffi
ffllil!lil,"o:?,T::_,1fi *;t;i^#;, iiffi;
..
,JI:#:::J""X,^nIlr:1\.",
,","r[T."rr';"florrr:T;r#Hiailv;
Refcrences
l. D. Feldman , Synthetic polymers,
Chapman Hall, 1996.
R' Sinha' ouyiiyls rtu*ir'irrinrrrogt,p..rii..
it-utt maiu, 2000.
3. M. Morron, Rubber
2'
r"ri"ri}.'
28
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY- SEMESTER IV
PAPER
XI.
PHYSICAL CHEMISTRY OF POLYMERS
(70 h)
uNrT r (r4 h)
Polymer chain structure and configuration, stereochemistry of repeating units, optical
isomerism, geometrical isomerism. Solution properties, polymer conformation and
chain dimensions, thermodynamics of polymer solutions, Flory-Huggins theory,
Folry-Krigbaum and modified Flory-Huggins theory, phase equilibria, solubility
parameter, intrinsic vi scosity. Mark-Houwink equation.
uNrT rr (6 h)
The amorphous state, conformation of the polymer chain, macromolecular dynamics.
The Rouse-Bueohe theory, Fickian and non-Fickian diffusions.
uNrT rrr (10 h)
The crystalline state, melting phenomena, crystal structure, unit cell, polyethylene and
other polyolelin polymers, liinged micelle model, polymer single crystal spherulites,
kinetics of crystallizalion.'l-he Avrami equation, efl'ect of chemical structure on the
melting temperature and fibre formation.
uNrT rv (9 h)
Liquid crystalline polymers, liquid crystalline mesophases, phase diagrams, liquid
crystal classification, lyotropic liquid crystalline chemical structure, thermotropic
liquid crystalline structure, side chain liquid crystalline structure, thermodynamics
and phase diagrams.
uNrT v (15 h)
Glass transition, dynamic mechanical behaviour through the five regions of
viscoelastic behaviour, methods of measuring glass transition temperature
(dilatometry, thermal methods, dielectric and magnetic methods), other transitions.
Influence of time, temperature, and frequency on these relaxations. Theories of glass
transition (free volume, kinetic and thermodynamic), effect of molecular weight and
chemical structure on the glass transition temperature, damping.
uNrr vr
(6 h)
Crosslinked polymers and rubber elasticity, rubber network structure, rubber elasticity
concepts, thermodynamic equation of state. Mooney-Rivlin equation, Flory-Rechner
equation.
uNrT vrr (10 h)
Polymer visco elasticity and rheology, stress relaxation and creep. Maxwell and
Kelvin elements, four parameter model, relaxation and retardation times, timetemperature superposition, polymer melt viscosity and its dependence on molecular
weight and shear. Normal stress difference.
References
1. P. C. Hiemenz, Polymer Chemistry, Marcel Dekker, New York.
2. L. H. Sperling, Introduction to Physical Polymer Science, Wiley Interscience.
29
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY_ SEMESTER
PAPER
XII.
IV
TETING AND CIIARACTERISATION OF POLYMERS
(70 h)
uNrT r (ls h)
Standards zrnd standards organizations, test methods and specifications,
preparation
co
poymermol wt'
vapour pressure
test pieces,
s for
of
polymers and aAditivei, density,
c determination and ebullioscopic method,
;sure method, sedimentation velocity method,
Iight scattering method, gel permeation chromatography.
uNrT rr (10 h)
Mechanical p-roperties of polymers, stress and strain, tensile properties,
compressive
properties, flexural properties, hardness, dynamic mechanical testing,
torsion
pendulam, DMA, rebond resilience i-mpact, charpy impact and
falling weight, long
term testing, creep, stress relaxation, friction ad wear, abrasion
testing.
uNrT rrr (8 h)
Electrical and optical properties, resistivity, dielectric strength, dielectric
constant,
dissipation f'actor, power factor, arc resistance, optical p.op"ii"., light
transmission,
clarity, haze, relectance, birefringes.
uNrT rv (8 h)
'l-hermal properties; thermal
conductivity, heat capacity, thermal expansion, vicat
softening point, heat deflexion temperature, Tg, Tm and other transitions.
DTA, DSC,
TGA, low temperature tests, brittleness test.
uNrr v
(6 h)
Flow properties of polymer merts and solutions, shear stress, shear rate, capillary
rheometer, cone and plate rheometer.
uNrr vr
(8 h)
Spectroscopic characterization of polymers: IR spectroscopy, Raman
spectroscopy,
NMR spectroscopy- chemical methods and identification of poly-"rs.
uNrT vrr (5 h)
Test on rubbers: Univulcanized rubbers, PRI, scorch and cure rate,
vulcanized
rubbers, heat ageing, flex cracking, heat build up.
uNrT Vrrr (10 h)
Environmental resistance, effect of liquids, water absorption, effect
of ozone, ozone
cabinet, weathering, environmental stress cracking, biological attack, fire
resistance,
radiation resistance, gas, permissibility.
References
l. R. P. Brown, Testing of Rubber, Applied Science publishers.
2. R. P. Brown, Hand Book oJ'plastics Test Methods.
3 ' Vishu Shah, Handbook of Plastics Testing technologlt,
John Wiley and Sons, l9g
4. Iyres, Mead, Rjly, Handbook of plastics Test Methids,Elite publishers.
30
1.
t\
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY- SEMESTEII IV
PAPER
XIII.
POLYMER TECHNOLOGY
(70 h)
uNIr I (12 h)
Introduction to polymer processing, Importance of additives, plasticizers, fillers,
stabilizers, flame retardants, colourants, antistatic agents and blowing agents.
Principles of plastic compounding, rubber compounding and thermostat
compounding. Mixing machines.
UNIT II (lo
h)
Extruders lor plastics and rubbers, twin screw extruders, extrusion process' die swell
and part 6imension control, operating parameters, extrudate defects, production of
PVC pipe, hose, wires, cables and film.
uNrT III (8 h)
plastir:s iniection moulding- dilTerent types of injection moulding machines. Details
'l-ypical
of the iniection moulding machine, clam systems, injection moulding cycle.
three place injection mould and its components. Rubber injection moulding.
UNIT IV (12 h)
Extrusion and injection moulding machines, the processes, the mould and die details.
Iltrocluction to ihermoforming, rotational moulding and calendaring. Compression
and transfer moulding processes, the details of the moulds. Casting with PVC
plastisols.
uNrT v (i0 h)
aramide'
Fibres fiorn cellulose ancl its derivalives, polyolefinic, polyester, polyamide,
in
carbon and glass fibres. Fibre spinning operations, different types of cords used
tyre industr"y, definition o1' denier, tex, tenacity, different types of twisting'
geotextiles.
UNIT VI
(8 h)
Adhesives and surface coatings- concepts and terminology, types of adhesives,
bonding and testing, pigments and paints, paint properties ind their evaluation.
UNIT VII (10 h)
Blends and composites- definition, criterion for selection of blend components,
preparation, comatibilizers, properties. Composite matrix materials, fibres used
polyme. composites, differeni processing methods (hand lay up, spray up, filament
winding, injection moulding, reaction moulding and pultrusion (introduction only).
References
l. M. Jones, Polymer Processing, Chapman and Hall'
2. W. C. Wake,'Adhesives and lhe Foimulation of Adhesive, Applied Science Publishers,
3.
London, 1976C. M. Blow, Rubber Technoktgy and Manufacture'
4.D.R.Paul,S.Newman,PolymerBlends,AcademicPress'
5. Handbook of Composites,ztrd Etln., Ed by S. T. Peters, chapman and Hill, 1998'
31
SYLLABU - PRACTICAL PAPERS
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY ( I &
PRACTICAL
I.
fI
Semesters)
INORGANIC CHEMISTRY
UNIT I
Separation and identification of four metal ions of which two are less
familiar
elements Iike w, Se, Te, Mo, ce, Th, Ti, zr,y, u and Li. (Eliminating
acid radicars
not present). Confirmation by spot tests.
UNIT
11
Volumetric Determinations using:
a) EDTA (Al, Ba, Ca, Cu, Fe, Ni, Co, hardness of water, etc.)
b) Pstimations,,involving quantitative separation of suitable tinu.y mixtures of ions
cu2*, Ni2*, Fe3*, zn2*, cut*, Mg'*, cnojt, iu, Ag, etc. in sorution by vorumetric,
gravimetric, colorimetric and electroanalytical methods.
c) Analysis of ores and alloys like dolomite, galena. ilmenite, monazite,
t'eldspar and
kaoline and two alloys.
Unit
III
Colorimetric determination of chromium, iron, manganese, nickel, and titanium
using
either Dubosque or photoelectrio colorimeter.
References
l'
2'
3'
4'
G'H' Jeffery, J. Bassett, J. Mendhl*t R. C. Denny, Vogel's Text book of
euanlitative
Chemical Analysis,5m Edn., ELBS, 19g9.
D A Skoog, M West, Analytical Chemistry,
Japan
?
Ltd., 1986.
An Introduction, 4tl' Edn., CBS publishing
E' J' Meehan, S. Bruckenstein,I. M. Kolthoft E. B. Sandell,
Quantitative Chemical Analysis,
Edn., The Macmillan Company,1969.
R' A' Day (Jr), A. L. Underwood, Quantitative Analysis,6n Edn., prentice
Hall of India,
4th
1993.
32
\
UNIVERSITY OF CALICUT
M.Sc. POLYMERCHEMISTRY
PRACTICAL II.
UNIT
(I & [
Semesters)
ORGANIC CHEMISTRY
I.
Laboratory Techniques
Methods of separatioa and purification of
organic compounds - fractional, steam
and
low-pressure distilrations, fractionar crysta[;tio"
and subrimation
UNIT lI. Qualitative Organic Analysis
Separation and identification of the c
ten) by
compon
chromat
UNIT
lll.
I
i
Organic preparations
pounds (at least six double stage_ including
ortant synthetic methods and reaction, ,r"h
Perkin, Reimer_Tiemann, Sandmeyer, and
d benzoin condensations. Selective ieduction
coupling, phthalein fusion, etc.
UNIT lY. Quantitative Organic Analysis.
Estimation of nitrogen by Kjeldahl method,
estimation of hydroxyl and carbonyl
groups, determination of iodine number and
saponification value of oils. Estimation
of reducing sugar, amines, phenors, esters, uitu.nin, (A
and c), drugs (aspirin,
paracetdmol).
References
l. B. S. Furnis, A. J. I{annaford, p.
w. G. Smith, A. R. Tatcher, vogers
cngman, 1989.
Textbook
of
istry, 1957.
rtory Manual of Organic Chemistry,3rd Edn.,
1957.
ic Analysis
erimental Organic Chemistry, Vol. I and II,
8'
R' srinivasan, Ed. photochemicar synthesis, vor.
I and II.
JJ
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY ( I &
PRACTICAL
III.
II
Semesters)
PHYSICAL CHEMISTRY
UNIT l. Colligative Properties
1. Molecular weight from depression by transition method- cooling curve method.
2.
3.
Molecular weight by cryoscopic method.
Molecular weight Rast method.
ll. Viscosity
1. Determination of viscosity of pure liquids (water, methanol, ethanol, glycerol,
UNIT
benzene, nitrobenzene, carbon tetrachloride).
2.
Determination of composition of binary liquid mixtures (benzene-nitrobenzene,
water-alcohol).
Determination of molecular weight of a polymer (polystyrene in toluene).
3.
UNIT
l.
[ll.
2.
3.
4.
5.
Conductivity Experimenls
Equivalent conductance of a weak acid- verification of Ostwald's dilution lawcalculation of dissociation constant.
Equivalent conductance of strong electrolytes (KCl). Verification of Onsagar
equation.
Activity coefllcient <>f Zn in 0.002M ZnSOqusing Debye-Fluckel limiting law.
Solubility product of a sparingly soluble salt (e.g., AgCl, BaS0q)
Conductometric titrations
(a) IICI vs NaOH
(b) (HCl+ CH3COOH) vs NaOH
(c) AgNO3 vs KCl.
UNIT lY. Potentiometry
1.
Electrode potentials of Zn and Ag electrodes in 0.1 M and 0.001 M solutions at 25 "C
and determination of standard potentials.
Mean activity coefficient of an electroanalyte at different molalities by EMF method.
2.
3. Dissociation constant of acetic acid by potentiometric titration.
4. Determination of strength of the given HCI solution by differential
5.
'
6.
potentiometric
titration.
Dissociation constant of acetic acid in DMSO, DMF, acetone and dioxane by titrating
with NaOH.
Potentiometric titrzrtion.
i)
Mixture of chloride and iodide.
iD Mixture of HCI and CHTCOOH.
UNIT Y. Chemicol Kinetics
1.
2.
3.
4.
5.
Specific reaction rate of acid catalysed hydrolysis of methyl acetate.
Temperature coefftcient and energy of activation of hydrolysis of methyl acetate.
Determination of Arrhenius parameters.
Saponification of ethyl acetate (titration/conductance method).
Inversion of cane sugar in presence of I{Cl by polarimetry.
Iodination of acetone- determination of order.
34
g
UNIT yl. Adsorption (3 experiments)
I'
2'
Verification of Freundlich and Langmuir adsorption isotherms.
Determination of concentration of acetic aoidioxalic acid
using lrreundlich and
Langmuir adsorption isotherms.
UNIT Yll. Phase Equilibria
1. Phase diagram of a simple eutectic system.
2- Phase diagram of a binary sorid system forming
3.
4'
a compound.
Phenol-water system, aniline-water system.
Ternary liquid system with one pair of partially miscible liquids (DMSo-benzenc-water,
acetone-chloroform-water, etc.).
References
l. A. Finlay, J. A- Kitchener, pracricar physicar Chemistry, l,ongman.
2. A. M. James, Practical physicul chemistry,J. A. churchil LtJ., 1961.
3. F. Daniel, J. w. williams, p. Bender, R. A. Alberty, c. D. cornwell, J. B. Ilarrirnan,
Experimenlal Physicol Chemistry, McGraw Hill, 197b.
4' W' G. Palmer, Experimental Physical Chemistry, 2nd Edn., Cambridge University press,
1962.
5' D. P. Shoemaker, C. W. Garland. Experimental Phy.sical Chemistry, McGraw Hill.
35
UNIVERSITY OF CALICUT
M.SC. POLYMER CHEMISTRY- IV
SEMESTER
PRACTICAL IV.
POLYMER CHEMISTRY-
I
UNIT I
l. preparation of nylon 66.
2. preparation of polymethylmetacrylaete (pMMA).
3' preparation of poylacryramide lfree raaiiat
foiy...iration).
4' preparation ofpolyacryramide uy ."ao, porii..rrutior.
5. preparation of glyptal resins.
6. preparation of linear polystyrene.
7. Preparation of crosslinked polystyrene.
8. preparation of urea formaljehyde resin.
9. preparation ofphenol_formaldlhyde resin.
10. Introduction to the practice of
rubbe.
" lffilo}Jl
*i*ing
on two ror_miil.
moulded rubber goods
iiE"
^u,r,
tensile test sheets etc.)
12. Casting.
I3. Introduction to the practice of injection
moulding.
14. Characterisation techniques_ DS-C,
l.GA. FT_f[.
UNIT TI.
Quantitative analysis of polymers.
Systematic anarysis of virgin poryrners
UNIT
( r 0 sampres
to be done).
III.
Quantitative anarysis of porymer products for the fiilers
used (3 to be done).
36
UNIVERSITY OF CALICUT
M.Sc. POLYMER CHEMISTRY (IV Semester)
PRACTICAL
V
POLYMER CHEMISTRY-
II
UNIT'1. Polymer (Physical)
l.
Osmometry: Determination of molecular weight of polymer by osmotic pressure
method (demonstration only).
2. Viscometry: Determination of molecular weight of polymers by viscosity
mflNurements of dilute solutions.
3. . Potentiometric titration by polyelectrolytic solutions.
4. pH measurements of polyelectrolytic solutions.
5. Chromatographic techniques for the analysis of polymers.
6. Measurement of thermal conductivity of a polymer sheet using Lee's disc method.
7. Test for latex: Dry rubber content, total solid content, ammonia content and pH.
8. Comparison of capacity of polymer solids by photometric method, transparency,haze,
gloss meter.
UNIT ll. Polymer Processing
l.
2.
Plastic processing.
(a) Injection moulding- Hand type.
(b) Compression moulding.
Measurement of mechanical properties.
(a) Specimen preparation of measurement of tensile strength, measurement
hardness, abrasion resistance.
(b) Testing of mechanical properties on universal testing machine.
(c) Testing of other mechanical properties of rubber vulcanized.
of
References.
1. Mc Safety, Laboratory Preparation of Macromolecular Chemistry, Mc Graw Hill,
1979.
2. Balladeer, Bares, Collies, Experiments in Polymer Science.
3. Braun, Chardon, Kern, Techniques of Polymer Synthesis and Characterisation, Wiley,
1971.
4. Relevant ASTM standards.
37
\.
t
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