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«M.Sc., DEGREE [Choice Based Credit System (CBCS)] Branch IV (A) CHEMISTRY (Specializations in Organic, Inorganic and Physical Chemistry) REGULATIONS ...»

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Reference Books

1. P.W. Atkins, Molecular Quantum Mechanics, Oxford University Press, Oxford,

2. M.W.Hanna, Quantum Mechanics in Chemistry, W.A.Benjamin Inc. London

3. S. Glasstone, Thermodynamics for Chemists, Affiliated East West Press, New Delhi 1960.

4. K.J.Laidler, Chemical Kinetics, Harper and Row, New York,1987.

5. R.G. Frost and Pearson, Kinetics and Mechanism, Wiley New York, 1961

6. R.K.Prasad, Quantum Chemistry, Wiley Eastern, New Delhi,1992.

7. A.W.Anderson, Physical Chemistry of Surfaces, Wiley - Interscience, Newyork, 1990.

CHE C06 THERMODYNAMICS AND ELECTROCHEMISTRY

–  –  –

UNIT- I Group theory-I Symmetry elements; symmetry operations; point groups - identification and determination; comparison of molecular and crystallographic symmetry; reducible and irreducible representations; direct product representation; orthogonality theorem and its consequences; character table. Hybrid orbitals in non-linear molecules – Examples: H2O, NH3, BF3, CH4 and XeF4. Determination of representations of vibrational modes in non-linear molecules such as water, ammonia, BF3, CH4 and XeF4.

UNIT-II Thermodynamics First law of thermodynamics; temperature dependence of enthalpies; Second law of thermodynamics; Gibbs-Helmholtz equation; Third law of thermodynamics. Free energy and entropy of mixing; chemical potential, partial molar volume and partial molar heat content. Variation of chemical potential with temperature and pressureGibbs-Duhem equation. Thermodynamics of ideal and real gases-fugacity, activity and activity coefficient.

UNIT- III Statistical thermodynamics Thermodynamic probability and entropy; Boltzman distribution law;

Maxwel-Boltzman, Bose-Einstein and Fermi-Dirac statistics; vibrational, rotational and electronic partition functions; calculation of thermodynamic functions and equilibrium constants; Theories of specific heats of solids; postulates and methodologies of non-equilibrium thermodynamics; linear laws; Gibbs equation;

UNIT-IV Non-equilibrium thermodynamics Thermodynamic criteria for non-equilibrium states; entropy production and entropy flow; entropy balance equations for different irreversible processes (heat flow, chemical reaction etc.); Non-equilibrium stationary states; microscopic reversibility; Onsager reciprocal theory.

UNIT-V Electrochemistry Mean ionic activity and activity coefficient of electrolytes in solutions; ideal and non- ideal solutions; excess functions; Hydration number; Debye-Huckel treatment of dilute electrolyte solutions; Debye-Huckel limiting law; Electrochemical cell reactions Electrode-electrolyte interface; electrokinetic phenomina; electrode kinetics;

Batteries-primary and secondary; fuel cells; corrosion and its prevention.

Text Books

1. V. Ramakrishnan and M.S. Gopinathan, Group theory in Chemistry, Vishal Publications,1988.

2. J. Rajaram and J.C. Kuriacose, Thermodynamics for Students of Chemistry, Lal Nagin Chand, New Delhi, 1986.

3. M.C. Gupta, Statistical Thermodynamics, Wiley Eastern, New Delhi,1990.

4. J. Rajaram and J.C. Kuriacose, Irreversible Thermodynamics, Lal Nagin Chand, New Delhi, 1989.

5. S.Glasstone, Introduction to Electrochemistry, Affiliated East west Press, New Delhi 1960.

Reference Books

1. F.A. Cotton, Chemical Application of Group Theory, John Wiley and Sons Inc.

New York,1971.

2. K.V. Raman, Group theory and its applications to Chemistry, Tata McGraw-Hill Publishing Company,1990.

3. R.P.H.Gasser and W.G.Richards, Introduction to Statistical

Thermodynamics, World Scientific, Singapore, 1995.

4. D.R. Crow, Principles and application of Electrochemistry, Chapman and Hall, 1991.

5. J.O.M. Bockris and A.K.N. Reddy, Electrochemistry, Vols. 1 and 2, Plenum, New York, 1977.

6. P.H.Rieger, Electrochemistry, Chapman and Hall, New York, 1994.

CHE C07 ADVANCED ORGANIC CHEMISTRY – ORGANIC SYNTHESIS

–  –  –

UNIT I Advanced Conformational Analysis Conformation and reactivity in steroids; Reactions of enols and enolates – reflex effect and conformational transmission; Stereochemistry of conjugate addition; Allylic strain; Transannular interactions; Concept of internal strain; Conformational rule.

Conformation, stability and reactivity of decalins and perhydrophenanthrenes;

Conformational analysis of carbohydrates – nomenclature, methods of determining conformations, anomeric effect and effect.

UNIT II Functional Group Interconversions Functional group interconversions involving C=O, CHO, OH, SH, COOH, C=C, NH2, COOR, CONHR, C-Cl and C-Br functional groups; Protection and deprotection of reactive sites.

UNIT III Retrosynthetic analysis and C-X disconnections An introduction to synthons and synthetic equivalents, disconnection approach.

The importance of the order of events in organic synthesis, one group C-X and two group C-X disconnections, chemoselectivity, reversal of polaritiy, cyclization reactions, amine synthesis.

UNIT IV Organic Synthesis: C-C disconnections One group C-C disconnections – Alcohols and carbonyl compounds, regioselectivity, alkene synthesis, Olefination of carbonyl compounds-Mc Murry’s method use of acetylenes and aliphatic nitro compounds in organic synthesis.





Two group C-C disconnections – Diels Alder reaction, Michael addition and Robinson annelation, Stark-Enamine reaction.

UNIT V Reagents in Organic Synthesis Use of the following reagents in organic synthesis and functional group transformations - Complex metal hydrides, Gilman’s reagent, lithium diisopropylamide (LDA), dicyclohexylcarbodiimide, 1,3-dithiane (reactivity umpolung), trimethylsilyl iodide, tri-n-butyltin hydride, DDQ, phase transfer catalysts, crown ethers, Merrifield resin, Wilkinson’s catalyst and baker yeast; Woodward and Prevost hydroxylation, Peterson’s synthesis.

Text Books

1. Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & sons, INC, 1994.

2. D. Nasipuri, Stereochemistry of Organic Compounds, New Age International Publishers, II Edn. 1994.

3. R.E. Ireland, Organic Synthesis, Prentice Hall, 1969

4. R.K. Mackie, D. M.Smith and R.A. Aatkin, Guide Book to Organic Synthesis, 2nd edn, Longman Scientific and Technical, London, 1990

Reference Books

1. E.L.Eliel, N.C. Alliger, S.J. Angyal and G.A. Morrison, Conformational Analysis, Interscience, NY, 1965.

2. P.S. Kalsi, Stereochemistry and Mechanism through solved problems, II Edn., New Age International Publishers, 1994.

3. R.O.C. Norman, Principles of Organic Synthesis, II Edn., Chapman and Hall, 1993.

4. S.Warren, Designing Organic Synthesis – A Programmed Introduction to Synthon Approach, Wiley, NY, 1978.

5. S.Turner, Design of Organic Synthesis, Elsevier, 1976

6. Raymond K. Mackie, David M.Smith and R.A. Aatkin, Guide Book to Organic Synthesis, Longman Scientific and Technical, London, 1990.

CHE C08 ADVANCED TOPICS IN ORGANIC CHEMISTRY

Hours L T P C

UNIT I Oxidation and reduction reactions Mechanism and study of the following reactions – oxidation with chromium, manganese, osmium, lead, ruthenium and selenium.

Reductions: catalytic hydrogenations, metal hydride reductions (LAH, NaBH and their derivatives) Metal-ammonium reductions, Selectivity in reductions.

UNIT II Advanced NMR Spectroscopy Non first order spectra – simplification of complex spectra, high fields, deutrium substitution, shift reagents, satellite peaks and spin decoupling; Dynamic NMR – hindered rotation, ring reversal, atomic inversion and valence tautomerization.

C, H coupling – relationship between J and s character; Nuclear Overhauser effect; 2D NMR with emphasis on the application of H-H COSY, NOESY and ROSY.

UNIT III Chiroptical Properties ORD and CD – Circular bireferengence and Circular dichroism; Plain dispersion curves - single and multiple cotton effect curves and their applications; Octant rule;

-haloketone rule; Comparison of ORD and CD and their applications.

UNIT IV Bioorganic Chemistry Characteristics of enzymes – mechanism of enzyme action; Chymotrypsin;

Biological energy – ATP as universal currency of free energy, NADH, NADHP and FADH2 as major electron carriers; Co-enzyme A as an universal carrier of acyl groups; Glycolysis – various stages of glycolysis and the enzymes involved; Citric acid cycle and Urea cycle – various stages of cycles and the enzymes involved; Link between glycolysis and citric acid cycle; Biological oxidation – mechanism of biological oxidation of glyceraldehydes-3-phosphate to 1,3-diphosphogylcerate as an example; biosynthesis of fatty acids.

UNIT V Vitamins and Antibiotics Chemistry of the following antibiotics: penicillin, streptomycin, chloromycetin, oxy tetracycline and griseofulvin; Detailed chemistry and physiological action of Vitamin A, ascorbic acid, thiamin, riboflavin and elementary aspects of Vitamin B12.

Text Books

1. P.S. Kalsi, Spectroscopy of Organic Compounds, Wiley Eastern Ltd. Madras, 1995.

2. William Kemp, NMR in Chemistry, Mac Millan, 1986.

3. R.O.C. Norman, Principles of Organic Synthesis, Second edn., Chapman and Hall, 1993.

4. R.E. Ireland, Organic Synthesis, Prentice Hall, 1969.

5. R.K. Mackie, D. M.Smith and R.A. Aatkin, Guide Book to Organic Synthesis, 2nd edn. Longman Scientific and Technical, London, 1990

6. Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & sons, INC, 1994.

7. C. Djerassi, Optical Rotatory Dispersion, Mc Graw Hill, 1960.

8. I.L. Finar, Organic Chemistry, Vol.II, Fifth edn. First Indian reprint, Pearson Education Asia Pvt. Ltd. 2000

9. A.L. Lehninger, Biochemistry, W.H. Freeman & Company, II Edn., 1975.

10. M.N. Hughes, The Inorganic Chemistry of Biological Processes, Wiley, London II edn., 1982.

11. Atta-Ur-Rahman and M.I. Choudhary, New Trends in Natural Product Chemistry, Gordon & Breach Science Publishers, I Edn., 1998.

Reference Books

1. M.R. Rifi and Frank H. Covitz, Introduction to organic electrochemistry techniques and applications in organic synthesis, Marcel Dekker, New York, 1978.

2. S.Warren, Designing Organic Synthesis – A Programmed Introduction to Synthon Approach, Wiley, NY, 1978

3. S.Turner, Design of Organic Synthesis, Elsevier, 1976

4. D.Nasipuri, Stereochemistry of Organic Compounds, IInd Edn, New Age International Publishers, 1994.

5. H.Singh and V.K.Kapoor, Organic Pharmaceutical Chemistry, Vallabh, Prakashan, 2001.

CHE C17 ADVANCED INORGANIC CHEMISTRY – ORGANOMETALLIC

CHEMISTRY

Hours L T P C

UNIT I Structure and Bonding Definition of organometallic compound; classification of organometallic compounds; the metal carbon bond types - ionic bond, covalent bond, electron deficient bond, delocalised bond, dative bond; metal carbonyl complexes - synthesis, structure and reactions of metal carbonyls; the nature of M-CO bonding, binding mode of CO; IR spectra of metal carbonyls, metal carbonyl anions, metal carbonyl hydrides, metal carbonyl halides; metal carbonyl clusters - Wades rule and isolobal relationship; metal nitrosyls; dinitrogen complexes; dioxygen complexes.

UNIT II Chemistry of Metal Alkyl Complexes

Metal alkyl complexes - stability and structure, synthesis by alkylation of metal halides, by oxidative addition, by nucleophilic attack on coordinated ligands; metal alkyl and 18 electron rule; reactivity of metal alkyls - M-C bond cleavage reactions, insertion of CO to M-C bonds, double carbonylation, insertions of alkenes and alkynes, insertions of metals with C-H bonds; alkylidene and alkylidyne complexes - synthesis of alkylidene complexes in low oxidation states and in high oxidation states, bonding in alkylidene complexes; synthesis and bonding in alkylidyne complexes; reactivity of alkylidene and alkylidyne complexes.

UNIT III Chemistry of Alkene and Alkyne Complexes Alkene complexes - synthesis of alkene complexes by ligand substitution, by reduction and by metal atom synthesis; bonding of alkenes to transition metals - bonding in diene complexes; reactivity of alkene complexes; ligand substitution reactions with nucleophiles - olefin hydrogenation, hydrosilation; Wacker process; C-H activation of alkenes; alkyne complexes - bonding in alkyne complexes, reactivity, alkyne complexes in synthesis - Cobalt catalysed alkyne cycloaddition.

UNIT IV Chemistry of Cyclopentadienyl, Allyl and Arene Complexes Cyclopentadienyl complexes – metallocenes - synthesis of metallocenes, bonding in metallocenes, reactions of metallocenes, Cp2Fe/Cp2Fe+ couples in biosensors, bent sandwich complexes, bonding in bent sandwich complexes, metallocene halides and hydrides; metallocene and stereospecific polymerization of 1-alkenes; cyclopentadiene as a non-spectator ligand; monocyclopentadienyl (half-sandwich) complexes; synthesis and structures of allyl complexes; arene complexes – synthesis, structure and reactivity of arene complexes; multidecker complexes.

UNIT V Homogeneous Catalysis by Transition Metal Complexes Organometallic compounds in homogeneous catalytic reactions-coordinative unsaturation, acid-base behaviour reaction, migration of atoms or groups from metal to ligand, insertion reaction, reactions of coordinated ligands; catalytic reactions of alkenes isomerisation of alkenes, hydrogenation, hydroformylation and hydrosilation of alkenes;

alkene polymerization and oligomerisation.

Text Books

1. Bockmann, Organometallics 1, complexes with transition metal-carbon

-bonds, Oxford science publications, Oxford, 1996.

2. Bockmann, Organometallics 2, complexes with transition metal-carbon

-bonds, Oxford science publications, Oxford, 1996.

3. J. Haiduc and J.J. Zuckerman, Basic Organometallic Chemistry, Walter de Gruyter, Brelin, 1985.



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