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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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Concept of Chirality; R,S nomenclature; Enantiotropic and diastereotopic atoms and groups; Enantio and Diastereo selective synthesis; Newer methods of asymmetric synthesis including enzymatic and catalytic nexus. E – Z isomerism; Determination of configuration of geometrical isomers.

Configuration and conformation; Conformational analysis of cyclohexane systems;

Stability and reactivity of conformers in mono and disubstituted cyclohexanes.

Geometrical isomerism in decalins.

UNIT II Photochemistry

Introductory theory-Jablanski diagram, Norrish type I and II reactions, study of photochemical reactions of carbonyl compounds, photooxidations, photoreductions, photocycloadditions and photorearrangements - di-pi-methane rearrangement.

Study of following reactions: Paterno-Buchi, Favorski, Fries, Barton

UNIT III Pericyclic Reactions

Selection rules and stereochemistry of electrocyclic reactions, cycloadditions and Sigmatropic shifts – applications of Frontier Molecular Orbital approach, Correlation diagram approach, Huckel-Mobius approach and perturbation molecular orbital approach; Sommelet-Hauser, Cope and Claisen rearrangements.

UNIT IV Molecular Rearrangements

Favorskii, Stork enamine, Mannich, Barton, Hofmann-Loffler-Freytag, Sharpio, Baeyer-Villiger, Chichibabin and ene reactions; Sharpless asymmetric epoxidation.

Hofmann, Schmidt, Lossen, Curtius, Beckmann and Fries rearrangements;

Reformatsky, Grignard and Wittig reactions; Robinson annulation.

UNIT V Carbohydrates, Peptides, Proteins and Nucleic Acids Pyranose and furanose forms of aldohexoses and ketohexoses; Structure and synthesis of maltose, lactose and sucrose.

Sequence analysis of peptides by chemical, enzymatic and mass spectrometric methods; Peptidisation methods like activated ester method, mixed anhydride method using reagents like DCC and Woodward reagent.

Classification of proteins; Primary, secondary and tertiary structures of proteins and their functions.

Nucleic acids – nucleosides and nucleotides, their chemistry including synthesis;

RNA and DNA; Functions of nucleic acids.

Text Books

1. Ernest L. Eliel, Stereochemistry of carbon compounds, T.M.H. Edn., Tata McGraw-Hill Publishing Company, 1962.

2. P.S.Kalsi, Stereochemistry – Conformation and Mechanism, New Age International (P) Ltd. VI Edn., 2005.

3. J.M.Coxon and B. Halton, Organic Photochemistry, Cambridge University Press 1974.

4. Jerry March, Advanced Organic Chemistry – Reactions, Mechanisms and Structure, IV Edn., John Wiley & Sons, 1992.

5. Paul de Mayo, Molecular Rearrangements, Vol.I, Vol. II, Interscience, NY, 1963.

6. I.L. Finar, Organic Chemistry, Vol.II, V Edn., First Indian reprint, Pearson Education Asia Pvt.Ltd., 2000.

Reference Books

1. D.Nasipuri, Stereochemistry of Organic Compounds, New Age International Publishers, 1994.

2. V.M. Potapov, Stereochemistry, MIR Publishers, Moscow 1979.

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

4. P.S. Kalsi, Stereochemistry and Mechanism through solved problems, Second Edition, New Age International Publishers, 1994.

5. Charles A. Depuy and Orville L. Chapman, Molecular reactions and Photochemistry, Prentice Hall of India Pvt. Ltd, 1972.

6. N.J.Turro, Modern Molecular Photochemistry, Benjamin/ Cummings, Menlo Park, California, 1978

7. R.T. Morrison and R.N. Boyd, Organic Chemistry, Allyn and Bacon Inc., 1983.

8. S.H.Pine, J.B. Hendrickson, D.J.Cram and G.S.Hammond, Organic Chemistry, IV Edn., McGraw-Hill Company 1980.

9. P.S.Kalsi, Organic Reactions and Mechanisms, II Edn. New Age International Publishers, 2000.

10. J.M.Harris and C.C. Wamser, Fundamentals of Organic Reaction Mechanisms, John Wiley & Sons, Inc. 1976.

CHE C03 CLUSTER COMPOUNDS AND NUCLEAR CHEMISTRY

–  –  –

UNIT I Structure and Bonding Van der Waals bonding, Hydrogen bonding; HSAB concept; polyacids Isopolyacids of V, Cr, Mo and W; Heteropolyacids of Mo and W (only structural aspects).

Inorganic polymers - silicates - structure, properties, correlation and application;

Molecular sieves; polysulphur nitrogen compounds and polyorganophosphazenes.

UNIT II Boron Compounds and Clusters Boron hydrides, polyhedral boranes, hydroborate ions- a general study of preparation, properties and structure; Carboranes - types such as closo and nido, preparation, properties and structure; Metallo carboranes - a general study; Metal clusters-chemistry of low molecularity metal clusters only, multiple metal-metal bonds.

UNIT III Nuclear Chemistry I

Nuclear structure - stability of nuclei, packing fraction, even-odd nature of nucleons, n/p ratio, nuclear potential, binding energy and exchange forces; shell model and liquid drop model; Decay of radio nuclei - rate of decay; determination of half-life period; Modes of decay - alpha, beta, gamma and orbital electron capture; nuclear isomerism; internal conversions; Q value; nuclear cross section; threshold energy and excitation functions.





UNIT IV Nuclear Chemistry II

Different type of nuclear reactions with natural and accelerated particles-transmutation, stripping and pick-up, spallation, fragmentation, fission;

Characteristic of fission reaction, product distribution and theories of fission; fissile and fertile isotopes - U235, U238, Th232 and Pu239; atom bomb; nuclear fusion - steller energy;

Synthesis of new elements; principles underlying the usage of radioisotopes in analysis – agriculture, industry, medicine, mechanism of chemical reactions; uses of radioisotopes in analytical chemistry; isotopic dilution analysis; neutron activation analysis and dating methods.

UNIT V Experimental Methods Cloud chamber, nuclear emulsion, bubble chamber, proportional counters, G.M.

Counter, Scintillation counters and Cherenkov counters. Particle accelerators - Linear accelerator, Cyclotron, Synchrotron, Betatron and Bevatron.

Text Books

1. H.J. Emelius and Sharpe, Modern aspects of Inorganic chemistry, Universal book Stall, New Delhi, 1989.

2. J.E. Huheey, E.A. Keiter and R.L. Keiter, Inorganic Chemistry- Principles of structure and reactivity, 4th edition, Pearson-Education, 2002.

3. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Wiley Eastern, 5th edition, 1988.

4. S. Glasstone, Source book of atomic Energy, Van Nonstrand Co., 1969.

5. H.J. Arniker, Essentials of nuclear chemistry, 2nd edition Wiley eastern Co.,1987.

Reference Books

1. E.L. Mutteri, Polyhedral boranes, Acadamic press, NY, 1975.

2. N.H. Ray, Inorganic polymers, Academic press, NY, 1975.

3. K.F. Purcell and J.C. Kotz, Inorganic Chemistry, WB Saunders Co. USA 1977.

4. G.S. Manku, Inorganic Chemistry, TMH Co., 1984.

5. A.K. Srivatsava and P.C. Jain, Elements of Nuclear Chemistry, S. Chand and Co., 1989.

6. G. Friedlander, J.W. Kennedy and J.M. Miller, Nuclear and Radiochemistry, Wiley, 1964.

CHE C04 COORDINATION CHEMISTRY

–  –  –

UNIT I Metal-Ligand Bonding 18 Electron rule; EAN rule, theories of coordination compounds - valence bond theory, crystal field theory - splitting of d-orbitals in different symmetries, crystal field stabilization energy, factors affecting the magnitude of 10 Dq, evidence for crystal field stabilization, spectrochemical series, site selection in spinels, tetragonal distortion from octahedral symmetry, Jahn-Teller distortion; Molecular Orbital Theory - octahedral complexes, tetrahedral and square planar complexes, pi bonding and molecular orbital theory, experimental evidence for pi-bonding.

UNIT II Electronic Spectra and Magnetic Properties

Term states of dn ions - microstates and their classifications, electronic spectra of coordination compounds - selection rules, band intensities and band widths; energy level diagrams of Orgel and Tanabe - Sugano diagram; spectra of Ti3+, V3+, Ni2+, Cr3+, Co2+, Cr2+ and Fe2+; calculation of 10Dq and B for V3+ (oct) and Ni2+ (oct) complexes.

Magnetic properties of coordination compounds - change in magnetic properties of complexes in terms of spin-orbit coupling; spin only moments of dn systems; temperature independent paramagnetism; spin cross over phenomena.

UNIT III Structure of Coordination Complexes

Structure of coordination compounds with reference to the existence of various coordination numbers - complexes with coordination number two, complexes with coordination number three, complexes with coordination number four - tetrahedral and square planar complexes, complexes with coordination number five - regular trigonal bipyramidal and square pyramidal; site preference in trigonal bipyramidal complexes, site preference in square planar complexes; coordination number six - distortion from perfect octahedral symmetry, trigonal prism; stereoselectivity and conformation of chelate rings;

coordination number seven and eight.

UNIT IV Stability and Stereochemical Aspects Stability of complexes - thermodynamic aspects of complex formation, factors affecting stability, stability correlations, statistical and chelate effects; Determination of stability constants - polarographic, photometric and potentiometric methods.

Stereochemical aspects - stereoisomerism in inorganic complexes, isomerism arising out of ligand distribution and ligand conformation, chirality.

Macrocyclic ligand types - porphyrins, corrins, Schiff bases, crown ethers, cryptates and catenands. (simple complexes).

UNIT V Reaction Mechanism of transition metal complexes

Energy profile of a reaction, reactivity of metal complexes, inert and labile complexes, kinetic application of valence bond and crystal field theories, kinetics of octahedral substitutions, acid hydrolysis, factors affecting acid hydrolysis, base hydrolysis, conjugate base mechanism, direct and indirect evidences in favour of conjugate mechanism, anation reactions, reactions without metal ligand bond cleavage.

Substitution reactions in square planar complexes, the trans effect, mechanism of the substitution reactions. Redox reactions, electron transfer reactions, mechanism of one electron transfer reactions, outer sphere type reactions, cross reactions and Marcus-Hush theory, inner sphere type reactions.

Text Books

1. J.E. Huheey, E.A. Keiter and R.L. Keiter, Inorganic Chemistry- Principles of structure and reactivity, 4th edition, Pearson-Education, 2002.

2. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Wiley Eastern 1988.

3. S.F.A. Kettle, Co-ordination compounds, ELBS, 1973.

4. M.C. Day and J. Selbin, Theoretical Inorganic Chemistry, Van Nostrand Co., NY. 1974.

5. K.F. Purcell and J.C. Kotz, Inorganic Chemistry, WB. Sanders Co., USA 1977.

6. D. F. Shriver, P. W. Atkins and C.H. Longford, Inorganic Chemistry, ELBS, 2nd edition, 1994.

7. R.B. Heslop and K. Jones, Inorganic Chemistry, Elsevier, 1976.

Reference Books

1. D. Bannerjea, Co-ordination Chemistry, Tata-McGraw Hill, 1993.

2. M.L. Tobe, Inorganic Reaction Mechanism, Nelson, 1972.

3. K. Burger, Coordination Chemistry Experimental Methods, Butterworths, 1973.

4. B.N. Figgis, Introduction to Ligand Fields, Wiley Eastern Ltd, New Delhi, 1976.

5. F. Basolo and R.G. Pearson, Mechanism of Inorganic Reactions, Wiley Eastern, 1967.

CHE C05 QUANTUM CHEMISTRY AND SURFACE PHENOMINA

–  –  –

UNIT-I Quantum Chemistry-I Planck’s Quantum theory - wave particle duality, Uncertainity principle; Operators and commutation relations- Linear and Hermitian operators. Postulates of quantum mechanics; The Schrodinger equation-Particle in a box (one, two and three dimensional systems).

UNIT-II Quantum chemistry –II Applications of quantum mechanics - harmonic oscillator, rigid rotator, hydrogen atom; Approximation methods-variation and perturbation methods, application to helium atom.

UNIT-III Quantum Chemistry-III Born-Oppenheimer approximation- VB and MO treatments of hydrogen molecule;

MO for polyatomic molecules; Concept of hybridization-sp, sp2 and sp3; Huckel pielectron theory and its applications to ethylene, butadiene and benzene; Idea of self consistent fields.

UNIT-IV Surface Chemistry Surface tension; solid-liquid interfaces; contact angle and wetting; Solid-gas interface; Adsorption of gases on solids-Freundlich, Gibbs, Langmuir, Temkin and BET adsorption isotherm; Surface area determination; electrical phenomena at interfaces;

micelles and reverse micelles - solublization and microemulsion.

UNIT-V Chemical Kinetics

Methods of determining rate laws; Theories of reaction rates - simple collision theory, ARR theory; treatment of unimolecular reactions (Lindemann-Hinselwood and Rice-Ramsperger-Kassel-Marcus[RRKM] theories); termolecular reactions; chain reactions; explosive reactions; Arrhenius and Eyring equations; Reaction rates in solution; salt effect and solvent dielectric constant; Homogeneous and heterogeneous catalysis; Enzyme catalysis- Michaelis-Menton kinetics; Fast reactions- study of kinetics by stopped flow technique, relaxation method, flash photolysis and magnetic resonance method.

Text Books

1. D.A. McQuarrie, Quantum Chemistry, University Science Books, Mill Valley, California, 1983.

2. J. Rajaram and J.C. Kuriacose, Kinetics and Mechanism of Chemical Transformations, MacMillan India Ltd. 1993.

3. P.W.Atkins, Physical Chemistry, Oxford University Press, Oxford, 1990.

4. D.A. McQuarrie, Text Book of Physical Chemistry, University Science Books, Mill Valley, California, 1983.

5. R.A. Alberty and R.J.Silbey, Physical Chemistry, John Wiley and Sons, New York, 1992

6. A.W.Adamson, Physical Chemistry of surfaces, 4th edn., Wiley - Interscience, Newyork, 1982.



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