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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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4. J. E. Huheey, Inorganic Chemistry – Principles of structure and reactivity, Harper International Edition, Harper and Rone, New York, 1978.

5. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 5th Edition, 1988.

Reference Books

1. W.L. Jolly, Modern Inorganic Chemistry, McGraw-Hill, 2nd edition, 1991.

2. K.M. Mackey and R.A. Mackey, Introduction to Modern Inorganic Chemistry, Prentice Hall, 4th edition, 1989.

3. F. Basalo and R,G. Pearson, Mechanisms of Inorganic Reactions, Wiley Eastern, 2nd edition, 1977.

4. D.F. Shriver P.W. Atkins and C.H. Long ford, Inorganic Chemistry, ELBS 2nd Edition, 1994.

CHE C18 ADVANCED INORGANIC CHEMISTRY - SOLID STATE AND

BIOINORGANICS

–  –  –

UNIT I Chemistry of lanthanides and Actinides Electronic configurations, physical and chemical properties, stable oxidation states, the lanthanide contractions, spectral and magnetic properties of the compounds of lanthanides and actinides in comparison with the compounds of transition metals;

Structure and bonding in highly coordinated lanthanide and actinide complexes; Uses of lanthanide compounds as shift reagents.

Actinides - Synthesis of elements; extraction of Th and U; technical production of Pu.

UNIT II Structure of Solids

Types of solids – NiAs, CdI2, Pervokite, Spinel-normal and inverse spinels, structures. Diffraction methods – X-ray diffraction, various methods of X-ray analysis of structure, X-ray diffraction pattern, X-ray scattering factor, results and uses of x-ray diffraction, limitations of x-ray diffraction. Comparison of x-ray, electron and neutron diffraction only.

UNIT III Band theory and defects in Solids

Metallic state; free electron and band theories; Non-stoichiometry point defects in solids - Schottky and Frenkel defects, linear defects; dislocations - effects due to dislocations; electrical properties of solids – insulators, intrinsic semiconductors, impurity semiconductors (n and P type) and superconductors.

UNIT IV Photo-electron Spectroscopy

Principle; theoretical-valence and core binding energies; PES of diatomic and polyatomic molecules (HCl, HBr, HI, CO, NH3, H2O and N3- ion); Koopman’s theorem;

chemical shifts in X-ray photoelectron spectroscopy; core electron PES, X-ray PES (ESCA); applications.

NMR Spectroscopy: Applications of F and P-NMR spectra of inorganic compounds; Lanthanide shift reagents; study of fluxional behaviour of molecules.

UNIT V Bioinorganic Chemistry

Metalloporphyrins - the porphyrin ring systems - Chlorophyll, cytochromes;

Oxygen carriers - haemoglobin and myoglobin; Ferridoxins and rubredoxins; enzymes;

vitamin B12 and B12 coenzymes - structure and function; synthesis model of enzyme action - Inhibition and poisoning; Nitrogen fixation; Biochemistry of essential and trace elements in biological systems.

Text Books

1. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Wiley Eastern (P) Ltd., 1988.

2. E.A.V. Ebsworth, D.WH. Rankine and S. Craddock, Structural methods in Inorganic Chemistry, Black well Scientific Publ., 1987.

3. R.S. Drago, Physical Methods in Chemistry Reinhold, New York, 1968.

4. D. M. Adams, Inorganic Solids, John Wiley Sons, 1974.

5. A. R. West, Basic Solid State Chemistry, John Wiley Sons, 1991.

6. S.J. Lippard and Berg, Principles of Bioinorganic Chemistry, Univ. Science Books 1994.

7. D.E. Fenton, Biocoordination Chemistry, Oxford Science Publication 1995.

Reference Books

1. C.N.R. Rao and J.R. Ferraro, Spectroscopy in Inorganic Chemistry, Methven Co., London, 1968.

2. HAO. Hill and P. Day, Physical Methods in Adv. Inorganic Chemistry, John Wiley, 1986.

3. G.W. King, Spectroscopy and molecular structure, Holt Rienehart and Winston, 1964.

4. A.R. West, Solid state chemistry and its applications, Wiley, New York, 1984.

5. A. Muller, Inorganic Structural Chemistry, Wiley, New York, 1993.

6. J. A. Cowan, Inorganic biochemistry, Wiley-VCH, New York, 1997.

7. W.E. Addision, Structural principles of Inorganic Chemistry, Longman, 1961.

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

CHE C22 ADVANCED KINETICS AND PHOTOCHEMISTRY

Hours L T P C

UNIT – I Advanced Chemical Kinetics Activated complex theory; Reaction coordinates; transmission coefficient;

quantum mechanical tunneling; kinetic isotope effect; potential energy surfaces; influence of pressure on solution reactions; molecular cross sections and rate coefficients;

reactions in crossed molecular beams; Shock tube technique; Marcus theory of electron transfer reactions.

UNIT – II Advanced Catalysis

Micellar effects on organic reactions; kinetics of excited state processes in micellar media and reverse micelles; photocatalytic aspects of semiconductor clusters and colloids; clays and zeolites; Catalysis of organic reactions, Electrochemical and photochemical applications.





UNIT- III Bioenergetics

Limitations of equilibrium thermodynamics; fluctuations; irreversible processes and steady states; irreversible thermodynamics of bio systems; energy flux; ATP and its role in bioenergetics; role of singlet oxygen in biology; membrane potentials; ion pumps;

photoacoustic effect and its applications in biology.

UNIT – IV Photochemistry

Photochemical principles - absorption and emission of radiation, Franck-Condon principle; reaction paths of electronically excited molecules; Radiative and non-radiative processes-Jablanski diagram; fluorescence and phosphorescence; Chemiluminescence;

principles of laser action; Flash and laser photolysis; Quantum yield and actinometry;

properties of excited states - excited state acidity constants, dipole moments and redox properties; excimers and exciplexes; quenching processes and quenching mechanisms electron transfer and heavy atom quenching; Stern Volmer equation;

UNIT – V Photochemistry and Radiation Chemistry Photochemical reactions; Sources of ionizing radiations; dosimetry; radiolysis of water; pulse radiolysis. - photovoltaic and photo galvanic cells; photo electrochemistry;

prospects of solar energy conversion and storage.

Text Books

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

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

3. A.R.West, Solid State Chemistry and its applications, John Wiley and Sons, New York, 1984.

4. K.K.Rohatgi Mukherjee, Fundamentals of photochemistry, Wiley Eastern Ltd.,New York, 1978.

5. A.L.Lehninger, Bioenergetics, W.A.Benjamin Inc.,New York, 1965.

6. W.Hoppe, W.Lohmann, H.Markl and H.Uiegler, Biophysics, Springer-Verlag, 1983.

Reference Books

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

2. C.Capellos and B.H.J.Bielski, Kinetic Systems, Wiley Interscience, New York, 1968.

3. G.M. Harris, Chemical Kinetics, D.C. Healthand Co., 1966.

4. N.J.Turro, Modern molecular photochemistry, Benjamin/Cummings, Menlo Park, California, 1978

CHE C23 ADVANCED TOPICS IN PHYSICAL CHEMISTRY AND SPECTROSCOPY

Hours L T P C UNIT – I Advanced Quantum Chemistry Hartree and Hartree –Fock SCF methods-application to He atom; Electron correlation; Roothan and Hartree schemes for polyatomic molecules; HMO method and its applications; PPP method and CNDO approximations.

UNIT – II Advanced NMR Spectroscopy NMR in solids - magic angle spinning; analysis of complex NMR spectra - AB spectrum; NMR of paramagnetic compounds; Nuclear Overhauser effect; INDOR, CIDNP; 13C spectra - decoupling techniques; 2-dimensional NMR, COSY and NOESY.

UNIT – III Advanced ESR Spectroscopy ESR - first and second order spectra of hydrogen atom; ESR spectra of organic radicals; mechanism of hyperfine coupling; electron spin-spin interaction; triplet energy levels; half filled transitions; ENDOR; study of molecular rate processes; time scales of magnetic resonance experiments.

UNIT – IV Advanced Electrochemistry Wien and Debye-Falkenhagen effects; Debye-Huckel-Onsager equation;

transport properties in solution; diffusion and ionic mobility; Planck-Henderson equation;

Onsager’s reciprocity relations; zeta potential; polarisable and non-polarisable interfaces;

dynamic electrochemistry - electrode processes; non-equilibrium electrode potential;

polarization and over potential; Butler-Volmer equation; Tafel equation; Principles and applications of polarography, amperometry and cyclic voltammetry.

UNIT – V Solid State Chemistry Elements of crystallography-laws of crystallography, space lattices and unit cells;

crystal systems of lower symmetry and point groups; translational symmetry elements and space groups; X-Ray diffraction-mechanism, Bragg’s method, rotating crystal method and powder methods of XRD; Interpretation of diffraction pattern.

Text Books

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

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

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

4. C.N. Banwell, Fundamentals of Molecular Spectroscopy, Mc Graw Hill, New York, 1966.

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

6. A.L.Lehninger, Bioenergetics, W.A.Benjamin Inc.,New York, 1965.

7. W.Hoppe, W.Lohmann, H.Markl and H.Uiegler, Biophysics, Springer-Verlag, 1983.

8. A.Walton, Molecular and Crystal Structure Models, Ellis Horwood, Chichester, 1978.

9. F.C.Phillips, An Introduction to Crystallography, John Wiley and Sons, New York, 1963.

Reference Books

1. I.N. Levine, Quantum Chemistry, Allyn and Bacon, Boston, 1983

2. H. Eyring, J. Walter and G.Kimball, Quantum Chemistry, John Wiley and Sons, New York, 1944.

3. M.W. Hanna, Quantum Mechanics in Chemistry, W.A. Benjamin Inc. London, 1965.

1. G.M.Harris, Chemical Kinetics, D.C.Healthand Co., 1966.

2. B.Viswanathan, Catalysis: Principles and applications, Narosa Publ. New Delhi, 2004.

3. A. Carrigton and A.D. Mc Lachlan, Introduction to Magnetic Resonance, Harper and Row, New York 1967.

4. C.W.King, Holt, Spectroscopy and Molecular Structure, Rienehart and Winston, 1964.

5. Raymond Chung, Basic principles of spectroscopy, McGraw Hill Ltd, New York,1971.

6. D.R. Crow, Principles and applications of Electrochemistry, Chapman and Hall, 1991.

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

8. E.Conn and K.Stump, Outlines of Biochemistry, John Wiley and Sons, New York, 1987.

9. F.M.Harolg, The vital force: A study of Bioenergetics, W.H.Freennan &Co, New York, 1987.

CHE C09 SPECTROSCOPY

–  –  –

UNIT I Molecular Spectroscopy Interaction of matter with radiation, rotational, vibrational and electronic spectroscopy, Microwave, IR, Raman, UV-Visible- theory & instrumentation; rigid rotor, harmonic oscillator and anharmonicity; selection rules; vibrational spectra of polyatomic molecules, vibration frequencies, coupling, overtones, Fermi resonance.

UNIT II NMR Spectroscopy

NMR spectroscopy - theory & instrumentation, Zeeman effect, chemical shift, spin-spin coupling, NMR of simple AX and AMX type molecules, calculation of coupling constants, 13C-NMR- Fourier Transformation, resonance coupled and decoupled spectra;

2D NMR, COSY, NOESY.

UNIT III Mass and Mössbauer Spectroscopy Mass spectra – theory and instrumentation, McLafferty rearrangement fragmentation pattern. Mössbauer spectroscopy - Doppler effect, isomer shift, electron-neutron hyperfine interactions, Quadrupole interactions and magnetic interactions;

UNIT IV ESR Spectroscopy ESR Spectroscopy-theory and instrumentation- line width, the ‘g’ values, factors affecting the magnitudes of g and A tensors, zero field splitting and Kramer’s degeneracy.

UNIT V Applications of spectroscopy Applications of UV, VIS, IR, Raman, NMR and Mass spectral data for the structural elucidation of Organic and inorganic molecules. Problems involving the above spectral data to be worked out in detail. Applications of ESR to few biological molecules containing Cu(II), Fe(II) and Fe(III); Jahn-Teller distortions in Cu(II) complexes; simple applications of Mossbauer spectroscopy to Iron and Tin compounds.

Text Books

1. R.M Silverstein, C.G. Bassler and Morril, Spectrometric identification of organic compounds, VI Edn., John Wiley & Sons, New York, 2002.

2. P.S. Kalsi, Spectroscopy of organic compounds, Wiley Eastern Ltd., Madras, 1995.

3. C.F. Banwell, Fundamentals of Molecular Spectroscopy, McGraw Hill, New York, 1966.

4. R.S. Drago, Physical methods in chemistry, Reinhold, New york,1968.

Reference Books

1. G.M.Barrow, Introduction to Molecular Spectroscopy, McGrawHill, NewYork, 1962.

2. J.R.Dyer, Application of absorption spectroscopy of organic compounds, Prentice Hall of India Pvt. Ltd., New Delhi, 1974.

3. William Kemp, Organic Spectroscopy, ELBS, New Delhi, 1982.

4. A.Carrigton and A.D.McLachlan, Introduction to Magnetic Resonance, Harper and Row, New York 1967.

5. William Kemp, NMR in Chemistry, MacMillan Ltd., 1986.

6. C.N.R.Rao and J.R.Ferraro, Spectroscopy in Inorganic Chemistry, Methven Co., London, 1968.

7. Raymond Chang, Basic Principles of Spectroscopy, Mc Graw Hill Ltd., New York, 1993.

8. E.A.V. Ebsworth, D.WH. Rankine and S. Craddock, Structural methods in Inorganic Chemistry, Black well Scientific Publ., 1987.



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