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INDIAN INSTITUTE OF TECHNOLOGY MADRAS
DEPARTMENT OF CHEMISTRY
SYLLABUS FOR Ph.D. COMPREHENSIVE EXAMINATION
WRITTEN AND ORAL
JANUARY 2005
Ph.D COMPREHENSIVE EXAMINATION
SYLLABUS
WRITTEN EXAMINATION
(Compulsory for all Ph.D students irrespective of their research
areas)
ORAL EXAMINATION
1. PHYSICAL CHEMISTRY: For scholars in Physical
Chemistry.
2. THEORETICAL CHEMISTRY: For
Spectroscopy, Theoretical Chemistry.
scholars
in
3. INORGANIC CHEMISTRY: For scholars in Inorganic
chemistry.
4. ORGANIC
Chemistry.
CHEMISTRY:
For
scholars
in
5. BIOCHEMISTRY: For scholars in Biochemistry.
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Organic
WRITTEN EXAMINATION
I.
PHYSICAL AND THEORETIAL
CHEMISTRY
Atomic structure and Bonding:
Bohr’s model – results of wave mechanical model –
quantum numbers – shapes of orbitals – hybridisation –
periodic table – ionic and covalent bonding – VB and MO
theories – VSEPR approach – MO theory of diatomics – weak
bonds.
Thermodynamics and thermochemistry:
I and II laws – Cy and Cp – Isothermal and adiabatic processes
– carnot cycle – entropy – Hess law – Kirchoff’s law.
Chemical kinetics and equilibrium:
Rates of reactions – 1st and 2nd order reactions – activation
energy – Kp, Kx, Kn, etc. – homogeneous chemical equilibria –
acids and bases – pKa of acid – solubility product etc.
Electrochemistry:
Conductance of electrolytes – transference – cells, half cells –
Nernst equation – simple applications of conductivity and
potentiometry.
3
II. INORGANIC AND ANALYTICAL CHEMISTRY
Analytical Chemistry:
Principles of volumetric and gravimetric analysis, organic
reagents in inorganic analysis, Principles of Instrumental
methods in analysis – neutron activation, isotope solution
analysis, spectrophotometry and flamephotometry.
Chemistry of main group elements:
A comparative account of the Chemistry of alkali, alkaline
earth metals, non-transition elements and rare gases.
Coordination chemistry:
Coordination components, isomerism, Principles of VB, MO
and LF approaches, eleectronic spectrum and magnetic
properties.
Solid State Chemistry:
Crystal systems, structure of CsCl, CaF2, TiO2, diamond and
graphite, Electronic properties of solids, hand theory.
III. ORGANIC CHEMISTRY
IUPAC system of nomenclature, alkanes, alkenes, dienes,
ketones, alcohols, amines and carboxylic acids – their
preparation and properties.
4
Reaction Mechanism:
Elementary treatment of reaction of of type SN1, SN2, E1 and
E2. Hoffmann and Saytzeff Rules – substitutions at the
aromatic ring electrophilic, nucleophilic and radical –
correlation of structure and reactivity – inductive and
resonance and steric effects.
Aromalicity and benzene chemistry:
Studies of rearrangements (Wagner, Claisen, Cope, Fries)
Stereo Chemistry:
Cyclohexane – Conformational analysis geometric isomerism
concepts of Z and E, R and S notations.
General Chemistry:
Heterocyclic compounds: thiophene, pyrrole
Aminoacids: Methods of preparation of simple acids –
properties etc.
Simple ideas of application of spectroscopy.
IV. BIOCHEMISTRY
General considerations:
Cells – organization – supramolecular assembly – specialized
functions of subcellular organelles. Differential centrifugation
for organelle separation; Relevance of water – ionic product of
water – pH – buffers – Henderson Hasselbach Equation. Basic
chemical concepts related to thermodynamics – chemical
kinetics etc. Definition of enthalpy, Gibbs free energy, rate of
reaction – Nernst equation.
5
Biomolecules:
Basic chemical consideration of structure – bonding and
conjugation with regard to: Monosaccharides and
carbohydrates. Derivaties of sugars – simple and conjugated
poly-saccharides of biological interest – aminosugars – cell
wall components. Amino acids, peptides and proteins.
Classification – nomenclature – acid base properties and other
reactions – peptide bonds – peptides of importance – structural
aspects – alpha – helical and beta – pleated structures – tertiary
and quaternary structures – structural proteins – fibrous
proteins – collagen – globular proteins – oligomers – fatty
acids, triacyl glycerols, phospholipids, Sphingolipids and other
simple lipids – Nucleic acids, nucleotides, organization and
structure of DNA and RNA.
Enzymes:
General concepts in enzyme catalysis – effect of pH
temperature etc. – classification – cofactors and coenzymes –
vitamins – structure and function as cofactors – trace elements
as cofactors – mode of enzyme action – activation energy –
rate of enzyme action – activation energy – rate of enzyme
catalysed reactions – Michaelis Menton Equation and Km –
single substrate – bisubstrate reactions and kinetic analysis –
enzyme inhibition – competitive, noncompetitive and
incompetitive – allosteric enzymes – isoenzymes – enzyme
regulation – general methodology in purification identification
and characterization of proteins and enzymes – methods of
sequence analysis – principles of ultracentrifugation –
chromatography – some applications of spectroscopic methods
and isotope analysis.
6
Intermediary Metabolism:
Carbohydrate metabolism: Glycolysis – TCA cycle –
glyoxylate cycle – HMP shunt – anaerobic carbohydrate
metabolism.
Photosynthesis Lipid Metabolism: Oxidations including beta
oxidation and ketone bodies – electron transport chain and
oxidative phosphorylation.
Amino acid metabolism: General
transamination – urea cycle.
mode of degradation –
Nucleic acid: Concepts in nucleic acids – metabolism –
biosynthesis of nucleic acids – genetic code – protein
synthesis.
Regulation:
Regulatory concepts at gene level and protein/enzyme level.
Reference Books:
1. Daniels and Alberty, Physical Chemistry, Wiley Eastern.
2. F.A. Cotton and G. Wilkinson, Basic Inorganic Chemistry,
Wiley Eastern.
3. R.T. Morrison & R.N Boyd, Text Book of Organic
Chemistry, Prentice Hall of India.
4. A.L. Lehinger, Principles of Biochemistry, CBS Publishers,
Indian Edition 1984.
5. L. Stryer, W.H. Biochemistry, Freeman & Co.
7
ORAL EXAMINATION
I. PHYSICAL CHEMISTRY
(For research scholars in Physical Chemistry)
Thermodynamics:
First, second and third laws of thermodynamics and their
applications – free energy and chemical potential – chemical
equilibria – phase equilibria – surface chemistry and
thermodynamics – adsorption – solid state chemistry with
reference to adsorption – solution chemistry – colligative
properties – solvation – polar solvents.
Chemical Dynamics:
Kinetic theory of gases – kinetics of reactions in the gas phase
– basic relationships – theories of reactions – collision theory –
transition state theory – applications of thermodynamic
concepts to reactions – complex reactions such as parallel,
consecutive and reversible reactions – chain reactions and their
kinetics – kinetics in the liquid phase – effect of medium on
reactions – homogeneous and heterogeneous catalysis –
photochemistry in the gas phase and in solution – fluorescence
– mechanism of photochemical reactions – free radical and
ionic intermediates and their role in kinetics – irreversible
processes in solution – fast reactions – relaxation methods and
techniques – viscosity – diffusion – sedimentation – behaviour
of large molecules in solution – polyelectrolyes – surfactants
and their properties – supermolecular assemblies such as
colloids – gels.
8
Electrochemistry:
Electrochemical cells – Nernst equation – theory of strong
electrolytes (Debye-Huckel theory) – electrical double layer
Lippman equation and structure – electrokinetic phenomena –
basic electrode kinetics – Butler Volmer equation – Tafel
equation – electroanalytical techniques (e.g polarography etc.)
Text Books:
1.
2.
3.
4.
Walter J. Moore, Physical Chemistry
R.A Alberty, Physical Chemistry, VI Edition.
P.W. Atkins, Physical Chemistry, II Edition
A.W Adamson, Physical Chemistry
II. THEORETICAL CHEMISTRY
(For scholars in Spectroscopy, theoretical chemistry)
Quantum chemistry and Chemical bonding:
Schroedinger equation
(SE)
- postulates of quantum
mechanics – operators – operators (Hamiltonian, angular
momentum, spin and ladder) – exact solution of SE for some
systems eg. Particle in the box, rigid rotor harmonic oscillator
– approximate methods, variations and perturbation methods –
LCAO – MO and VB methods. MO of diatomics and
correlation diagrams – Huckel MO (HMO) theory and
application to simple systems (eg.conjugated polyenes etc.)
hybrid orbitals, molecular geometry.
9
Group theory:
Point groups – representations – character tables – direct
product rule – group theoretical selection rule in electronic, IR
and Raman Spectroscopy – application to hybridisation, MO
theory and ligand field theory.
Spectroscopy:
UV-Vis, IR, Raman spectroscopy – principles of NMR and
ESR spectroscopy – spin – spin splitting – hyperfine
interactions – fundamental understanding of ESCA and Moss
bauer spectroscopy - theories of the above spectroscopies
with quantum mechanical approach – applications.
Test Books:
1. Jra N. Levine, Quantum chemistry Vol.I and II.
2. P.W. Atkins, Quantum Mechanics.
III. INORGANIC CHEMISTRY
(For research scholars in Inorganic Chemistry)
Synthetic Inorganaic Chemistry:
Synthesis, principles and structures of the following
compounds, boron hydrides, boron anions , carboranes,
compounds having B-N, B-P, Si-O, P-N, S-N, metal-hydrogen
and metal carbon bonds – noble gas compounds.
10
Coordination compounds and transition metals:
Coordination number – nomenclature – measurement of
stability constants of complexes – mono and polyligated
systems. Reaction mechanism of square planar and octahedral
complexes.
dn configurations and their theoretical analysis R – S states –
CF and LF theories – state splitting in different fields. Orgel
diagram – Sugano-Tanabe approaches. Electronic spectra of
complexes.
Lanthanides – their properties – spectral and magnetic
properties of lanthanides and transition and metal complexes.
Organo-Metallics:
Metal carbonyls – olefin and acetylene complexes –
metallocenes – hemoglobin.
Solid State Chemistry:
Crystal symmetry, structure of simple compounds, electronic
and magnetic properties of solids.
Nuclear and Analytical Chemistry:
Nuclear reactions – fission and fusion – Radioactive decay
process – interaction of radiation with matter – activation
analysis – treatment of analytical data – general applications of
instrumental methods of chemical analysis – electrochemical
and spectroscopic methods in analytical chemistry.
11
IV. ORGANIC CHEMISTRY
(For research scholars in Organic Chemistry)
Reaction Mechanism:
Chemical bonding and structure – linear free energy
relationships – nucleophilic substitution reactions at saturated
carbon atoms – neighbouring group participation – carbonium
ion rearrangements – mechanisms of oxidation of alcohols and
ketone reductions.
Stereochemistry:
Optical activity – asymmetric synthesis – conformational
analysis of cyclohexanes and decalines – octant rule.
Reactions:
Cycle additions – hydroboration – Hunsdiecker, Dieckmann
and Claisen rearrangements and their mechanism – electron
deficient carbon and nitrogen mediated rearrangements –
Witting, Wolff, Hoffmann, Curtius, Schmidt rections –
Mannich, Favorski, Michael, Robinson reactions – enolates
and enamines.
Organic Photochemistry:
Reactions of carbonyl compounds – dienes, cycloadditions etc.
– Woodward –Hoffmann rules – applications.
12
Terpenes and Steroids:
Terpenes: Classification – syntheses – structural elucidation of
monoterpenoid and diterpenoids.
Steriods: Classification – rearrangements of steroids – photo
chemical transformations – Barton reaction – cholesterol –
synthesis of only aromatic steroids.
Structural Elucidation by Spectroscopic Methods:
Application of UV, IR, NMR and ORD spectroscopy to
structural analysis of organic compounds.
Test books:
1.
2.
3.
Jerry March, Advanced Organic Chemistry –
Reactions, mechanism and structures, McGraw
Hill.
I.L Finar, Organic Chemistry, Vol.II, ELBS –
Longman
R.M. Silverstein, G.C. Bassler, T.C Morril,
Spectrometic Identification of Organic Compounds,
IV Edn., John Wiley.
13
V. BIOCHEMISTRY
(For research scholars in Biochemistry)
Chemistry of Biological Compounds:
pH and buffers: Carbohydrates; lipids; amonoacids and proteins,
nucleic acids and their componets, biochemical energetics,
enzymes, vitamins and coenzymes.
Metabolism of Energy-yielding Compounds:
The cell – its biochemical organization, anaerobic carbohydrate
metabolism, alternate routes of glucose catabolism, the
tricarboxylic acid cycle, lipid metabolism, electron transport and
oxidative phosphorylation, photosynthesis, the nitrogen and sulfur
cycles, the metabolism of ammonia and nitrogen containing
monomers.
Metabolism of Informational Molecules:
Biosynthesis of nucleic acids, genetic code, genetic engineering,
biosynthesis of proteins, metabolic relation.
Methods of Biochemistry:
pH and its measurement – design of glass electrode, isotopic
methods,
spectrophotometry,
principles
of
grating
spectrophotometer,
filter
colorimeter,
fluorimeter,
chromatography principles, separation by gas, paper, thin-layer,
ion exchange, gel-filtration and HPLC, ultra centrifugation,
purification of enzymes and proteins, and protein sequencing.
14
Special Topics in Advanced Biochemistry:
Principles of Immuno Chemistry, applications of radio-immuno
ELISA etc., structure of prokaryotes and virus, nature and
function of steroidal and non-steroidal hormones.
Test book:
1. E.E. Conn and P.K. Stump, Outlines of biochemistry, Wiley
Eastern Ltd.
2. Lubert Stryer, Biochemistry, W.H. Freeman & Co.
3. Albert L. Lehninger, Principles of biochemistry, CBS
Publishers, First Indian Edition 1984.
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