Department of chemistry

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 scholars in Spectroscopy, Theoretical Chemistry.
   

3. 
   INORGANIC CHEMISTRY: For scholars in Inorganic chemistry.
   

4. 
   ORGANIC CHEMISTRY: For scholars in Organic Chemistry.
   

5. 
   BIOCHEMISTRY: For scholars in Biochemistry.
   

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WRITTEN EXAMINATION

1. 
   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 – C_y and C_p – Isothermal and adiabatic processes – carnot cycle – entropy – Hess law – Kirchoff’s law.
Chemical kinetics and equilibrium:
Rates of reactions – 1^st and 2^nd order reactions – activation energy – K_p, K_x, K_n, etc. – homogeneous chemical equilibria – acids and bases – pK_a of acid – solubility product etc.
Electrochemistry:
Conductance of electrolytes – transference – cells, half cells – Nernst equation – simple applications of conductivity and potentiometry.

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.

Reaction Mechanism:
Elementary treatment of reaction of of type S_N1, S_N2, 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.
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 K_m – 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.


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 mode of degradation – transamination – urea cycle.
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.
   

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.
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. 
   Walter J. Moore, Physical Chemistry
   
2. 
   R.A Alberty, Physical Chemistry, VI Edition.
   
3. 
   P.W. Atkins, Physical Chemistry, II Edition
   
4. 
   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.


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.

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.


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.


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. 
   Jerry March, Advanced Organic Chemistry – Reactions, mechanism and structures, McGraw Hill.
   
2. 
   I.L Finar, Organic Chemistry, Vol.II, ELBS – Longman
   
3. 
   R.M. Silverstein, G.C. Bassler, T.C Morril, Spectrometic Identification of Organic Compounds, IV Edn., John Wiley.
   

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.


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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