Detail course list for pg chemistry, Exercises of Chemistry

Download Detail course list for pg chemistry and more Exercises Chemistry in PDF only on Docsity! MANONMANIAM SUNDARANAR UNIVERSITY TIRUNELVELI M.Sc. CHEMISTRY SYLLABUS (Effective from the academic year 2017 – 2018 onwards) SEMESTER – I to IV Course Structure and Examination Under CBCS System Dr. S. SELVARAJ Chair Person PG Board of Studies - Chemistry Table – 4 : Common Course Structure for M.Sc. ( Chemistry) Degree programme (with effect from the academic year 2017-2018 onwards) Sem. (1) Sub. No. (2) Subject Status (3) Subject Title (4) Contact Hrs/ week (5) Credits (6) I 1 Core - 1 Organic Chemistry – I 4 4 2 Core - 2 Inorganic Chemistry – I 5 4 3 Core - 3 Physical Chemistry – I 5 4 4 Elective - 1 Advanced Topics In Chemistry – I 4 4 5 Core - 4 Practical - 1 Organic Chemistry Practical – I 4 2 6 Core - 5 Practical - 2 Inorganic Chemistry Practical – I 4 2 7 Core - 6 Practical - 3 Physical Chemistry Practical – I 4 2 Sub total 30 22 II 8 Core - 7 Organic Chemistry – II 5 4 9 Core - 8 Inorganic Chemistry – II 4 4 10 Core - 9 Physical Chemistry – II 5 4 11 Elective - 2 Advanced Topics In Chemistry – II 4 4 12 Core - 10 Practical - 1 Organic Chemistry Practical – II 4 2 13 Core - 11 Practical - 2 Inorganic Chemistry Practical – II 4 2 14 Core - 12 Practical - 3 Physical Chemistry Practical – II 4 2 Sub total 30 22 SECOND SEMESTER THEORY Components Sub.Code Contact Hrs / Week Credits Internal Marks External Marks Total Marks Passing Minimum External Total Core – 7 Organic Chemistry -II PCHM21 5 4 25 75 100 38 50 Core – 8 Inorganic Chemistry –II PCHM22 4 4 25 75 100 38 50 Core – 9 Physical Chemistry - II PCHM23 5 4 25 75 100 38 50 Elective – 2 Advanced Topics in Chemistry – II PCHE21 4 4 25 75 100 38 50 SECOND SEMESTER PRACTICAL Components Sub. Code Contact Hrs / Week Credits Internal Marks External Marks Total Marks Passing Minimum External Total Core – 10 Organic Chemistry practical –II PCHL21 4 2 50 50 100 25 50 Core – 11 Inorganic Chemistry practical-II PCHL22 4 2 50 50 100 25 50 Core – 12 Physical Chemistry practical- II PCHL23 4 2 50 50 100 25 50 SECOND YEAR (2017- 2018 onwards) THIRD SEMESTER THEORY Components Sub.Code Contact Hrs / Week Credits Internal Marks External Marks Total Marks Passing Minimum External Total Core – 13 Organic Chemistry -III PCHM31 5 4 25 75 100 38 50 Core – 14 Inorganic Chemistry -III PCHM32 5 4 25 75 100 38 50 Core – 15 Physical Chemistry- III PCHM33 4 4 25 75 100 38 50 Core – 16 Scientific- Research Methodology PCHM34 4 4 25 75 100 38 50 THIRD SEMESTER PRACTICAL Components Sub.Code Contact Hrs / Week Credits Internal Marks External Marks Total Marks Passing Minimum External Total Core – 17 Organic Chemistry practical –III PCHL31 4 2 50 50 100 25 50 Core – 18 Inorganic Chemistry practical-III PCHL32 4 2 50 50 100 25 50 Core – 19 Physical Chemistry practical- III PCHL33 4 2 50 50 100 25 50 FOURTH SEMESTER THEORY Components Sub.Code Cont. Hrs / Week Credits Internal Marks External Marks Total Marks Passing Minimum External Total Core – 20 Organic Chemistry -IV PCHM41 4 4 25 75 100 38 50 Core – 21 Inorganic Chemistry-IV PCHM42 4 4 25 75 100 38 50 Core – 22 Physical Chemistry-IV PCHM43 4 4 25 75 100 38 50 FOURTH SEMESTER PRACTICAL Components Sub.Code Contact Hrs / Week Credits Internal Marks External Marks Total Marks Passing Minimum External Total Core – 23 Organic Chemistry practical –IV PCHL41 4 2 50 50 100 25 50 Core – 24 Inorganic Chemistry practical-IV PCHL42 4 2 50 50 100 25 50 Core – 25 Physical Chemistry practical- IV PCHL43 4 2 50 50 100 25 50 Core-26 Project & viva- voce PCHP41 6+6* 6 0 100 100 50 50 *Extra hours for the project For the project, flexible credits are b/w 5-8 & Hours per week are b/w 10-16. Total number of credits ≥ 90 : 90 Total number of Core Courses : 26 (13T+12P+1Project) Total number of Elective Courses : 02 Total number of Courses : 28 Total hours : 120 FIRST YEAR M.Sc. CHEMISTRY SYLLABUS ORGANIC CHEMISTRY – I (Semester - I) Sub. Code: PCHM 11 2017-18/ MSU/46th SCAA/ Affiliated coll. /PG/M.Sc.,(Chemistry)/Sem.-1/Core-1/ Objectives: • To understand the concept of Aromaticity, Novel ring systems, Reaction Mechanism, stereochemistry and important reagents for synthetic uses. UNIT – I: AROMATICITY AND NOVEL RING SYSTEM Aromaticity: Benzenoid and non–benzenoid compounds – generations and reactions – sextet theory – MO theory – Huckel’s rule – Annulenes and hetero annulenes – Anti and homo aromaticity – Fullerenes. Novel ring system: Nomenclature of bicyclic and tricyclic systems – structure and synthesis of Adamantane – Congressane – Alternant and non – alternant – Azulene – and sydnones. UNIT – II: ORGANIC REACTION MECHANISM AND METHODS Reaction mechanism: Energy diagram of simple Organic reactions – Transition state and intermediate. Kinetic and Thermodynamic requirements of reactions –Baldwin rules for ring closure -Hammond Postulate and microscopic reversibility. Methods: Kinetic and Thermodynamic control of product formation. Kinetic methods of determination: Rate law – Primary and secondary isotope effect. Non-Kinetic methods of determination: Testing and Trapping of intermediates, isotopic labeling, Cross–over experiment and stereo chemical evidence. LFER: Hammett equation – Physical significance of σ and ρ – Applications and Limitations – Taft equation. UNIT – III: STEREOCHEMISTRY Concept of chirality: – Enantiotopic, diastereotopic hydrogens and prochiral centres – axial and planar chirality – stereochemistry of compounds containing two dissimilar asymmetric carbons, ansa compounds and para cyclophanes. R/S notations of Spiranes, allenes and Biphenyl ortho derivatives – E/Z notation of compounds containing one and two double bonds. Stereospecific and stereoselective synthesis – Methods of Asymmetric synthesis including enzymatic and catalytic process – Cram’s rule and Prelog’s rule – Cram chelation model and Felkin – Ahn model. UNIT – IV: REARRANGEMENT REACTIONS Types of rearrangements: Nucleophilic, electrophilic and Free radical and protrophic reactions. Mechanism: Nature of migration – migrating aptitude and memory effects, ring enlargement and ring contraction rearrangements. Reactions: Carbon to carbon migration: Wagner – Meerwein, Pinacol – Pinacolone, Benzil – Benzilic acid, Arndt – Eistert synthesis, Demjanov and dienone-phenol rearrangements. Carbon to oxygen migration: Baeyer–Villiger, Hydro peroxide and Dakin rearrangements. Carbon to Nitrogen migration: Lossen, Neber and curtius rearrangements. Miscellaneous: Von – Richter rearrangement and Fischer - Indole synthesis. UNIT – V: REAGENTS IN ORGANIC SYNTHESIS Gilman’s reagent – LDA – DCC – 1,3 – dithane (umpolung synthesis ) – Selenium dioxide. Fetizon’s reagent – Lemieux – Von Rudloff reagent – Lemieux–Johnson reagent – Woodward and prevost hydroxylation. Merrifield resin – Vaskas catalyst – Wilkinson’s catalyst. REFERENCES 1. P. Sykes, ‘A Guide book to mechanism in organic chemistry’, Orient Longman, 1989. 2. S.M. Mukherji and S.P. singh, ‘ Reaction mechanism in Organic Chemistry ‘, Macmillan India Ltd, 1978. 3. M. Mukerji, S.P. Singh, and R.P. Kapoor, “Organic chemistry”, Vol . I and II, Wiley Eastern Ltd., 1985. 4. J.March, ‘ Advanced organic chemistry’, Fourth Edition, John Wiley and Sons, Newyork, 2006. 5. I.L. Finar, ‘Organic Chemistry’, Vol I and II, ELBS, fifth Editon, 2001. 6. F.A. Carey and R.A Sundberg, ‘ Advanced Organic Chemistry’ (part A and B) plenum publishers, 2000. 7. E.S. Gould, ‘ Mechanism and structure in organic chemistry’ Holt, Rinehart and Winston Inc., 1959 8. S.H. Pine, ‘Organic Chemistry’ , 5th Edition, Mc Craw Hill International Edition, 1987. 9. E.L. Eliel, ‘Stereochemistry of Carbon compounds, Mc Craw Hill 1999. 10. E.L. Eliel and S.H. Wilen, ‘Stereochemistry of organic compounds’, John Wiley and sons, Inc., 2003. 11. P.S. Kalsi, ‘ Stereo chemistry – Conformation and mechanism – New Age international (p) Ltd., 2000. 12. P.Ramesh, ‘Basic Principles of organic stereochemistry’, Meenu Publications, Madurai, First Edition, 2005. 13. D. Nasipuri, ‘Stereochemistry of organic compounds – Principles and applications’, Wiley Eastern Ltd., 1991. 14. J.M. Harris and C. Wamser – John, ‘ Fundamentals of organic reaction mechanism – Wiley and sons 15. F.A Carey,’Organic Chemistry, Tata Mc Graw Hill, fifth reprint, 2005. 16. T.H. Lowry and K.S Richardson,’ Mechanism and Theory in Organic Chemistry’, Houper and Row Publishers – Newyork, 1987 17. V.M. Potapov, ‘Stereochemistry’ – Mir Publishers ,1979 18. R.O.C.Norman, ‘Principles of Organic Synthesis, Chapman Hall, London, 1993. 19. Raj K. Bansal, ‘Reaction mechanism in Organic chemistry, Tata Mc Graw Hill, Third Editon, 10th reprint, 2005. 20. Gurdeep R. Chatwal, ‘Reaction mechanism and Reagents in organic chemistry’, Himalaya publishing House, Bombay 1992. 21. J.N. Gurtu and R. Kapoor, ‘Organic Reactions and Reagents’, S.Chand and company Pvt. Ltd., 22. Gurdeep Chatwal,’Organic Chemistry of Natural Products,’ Vol.I and II, Himalaya Publishing House, Bombay 1992. 23. O.P. Agarwal, ‘Chemistry of Natural Products,’Vol I and II, Goel publishing House, Meerut, 1984. 24. V.K. Ahluwalia and R.K. Parshar, ‘Organic Reaction mechanism,’second Edition , Narosa publishing House,2005. 25. H.O. House, ‘Modern synthetic Reaction,’Second Edition , W.A. Benjamin, Inc., London, 1972. 26. R.K. Mackie, M.M. Smith and R.A. Aitken,’Guide Book to Organic Synthesis’ Second Edition, Longman Seientific and Technical, Singapore, 1990. 27. K. Nakanishi, ‘Natural Product Chemistry,’Blackie Publications, Vols, I, II, III. 28. R.H. Thomson, ‘Chemistry of Natural Products – Wiley, Newyork, 1996. 29. R.T. Morrison and R.N. Boyd,’Organic Chemistry’ sixth Edition, Prentice Hall, 1994. 30. Michael B. Smith, ‘Organic Synthesis,’ Mc Graw Hill international Edition , 1994. 31. Bhupinder Mehta, Manju Mehta, Organic Chemistry, PHI Learning, New Delhi, 2011. 32. Organic chemistry by Clayden, Greeves, Warren & Wothers. 33. Organic chemistry by John McMurry. 34. Organic chemistry by L.G. Wade. JR. 35. Named Organic reactions by Thomas laue & Andreas Plagens. ********** 3. D.F. Shriver, P.W. Atkins and C.H. Langford, Inorganic Chemistry, ELBS, Oxford University Press, 1994. 4. N.N. Greenwood and Earnshaw, Chemistry of the Elements, Pergamon Press, 2nd Edition, 1997. 5. K.F. Purcell and J.C. Kotz, Advanced Inorganic Chemistry, Saunders Golden Publishers, 1977. 6. B.E. Douglas, D.H. McDaniel and J.J. Alexander, Concepts and Models of Inorganic Chemistry, John Wiley and Sons Ltd. 2nd Edition, 1983. 7. J.D. Lee, Concise Inorganic Chemistry, ELBS, 2006. 8. Anthony R. West, Solid State Chemistry and its Application, Wiley, 2nd Edition, 2014. 9. T. Kutty, J. Tareen, Fundamentals of Crystal Chemistry, University Press, 1st Edition, 2001. 10. L.V. Azaroff, Introduction to Solids, Tata McGraw Hill Publishing Ltd., India, 1989. 11. C. Kittel, Introduction to Solid State Physics, Wiley Eastern Ltd., 5th Edition, 1993. 12. H.V. Keer, Principles of the Solid State, Wiley Eastern Ltd., 1993. 13. D.K. Chakrabarthy, Solid State Chemistry, New Age International. 14. A.F. Wells, Structural Inorganic Chemistry, Oxford Science Publication, London, 1979. 15. B. Sahoo, N. C. Nayak, A. Samantaray, P.K. Pujapanda, Inorganic Chemistry, PHI Learning, New Delhi, 2012. 16. Samuel Glasstone, Source Book of Atomic Energy, East West Pvt.Ltd., 1969. 17. H.J. Arnikar, Essentials of Nuclear Chemistry, Wiley Eastern Ltd., 4th Edition ,2000. 18. G. Friedlander, J.W. Kennedy, E.S. Macies and Julian Malcolm, Nuclear and Radiation Chemistry, Wiley Interscience publication, 1981. 19. Gregory Choppin, Jan-Olov Liljenzin, Jan Rydberg, Christian Ekberg, Radiochemistry and Nuclear Chemistry, Academic Press, 4th Edition, 2013. 20. Gregory Choppin, Jan Rydberg, Jan-Olov Liljenzin, Radiochemistry and Nuclear Chemistry, Butterworth–Heinemann, 2002. *************** PHYSICAL CHEMISTRY - I Semester - I Sub.Code:PCHM13 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-1/Core-3/ Objective: To learn the definitions of Partial molar properties and Phase rule. To understand the Principles of Thermodynamics of irreversible processes, Quantum mechanics and Statistical Thermodynamics UNIT-I Thermodynamics Concepts of Partial molar properties – Partial molar free energy, chemical potential, partial molar volume and its significance. Gibbs-Duhem equation, Gibbs-DuhemMargulus equation. Chemical Potential, Variation of Chemical Potential with temperature and Variation of Chemical Potential with pressure. Determination of partial molar volume: Graphical method, intercept method and Apparent molar volume method. Concept of Fugacity; Determination of Fugacity by graphical method and compressibility factor method, Fugacity of a liquid component in a liquid mixture, Physical significance of Fugacity. Activity and activity coefficient: Definition of activity and activity coefficient, determination of activity coefficient by EMF and solubility method. Thermodynamics of non ideal system-Excess thermodynamic function, GE, SE, HE etc. UNIT-II Phase Rule & Thermodynamics of irreversible processes: Lever rule, Derivation of Lever rule. Phase rule and compressed Phase rule, Derivation of phase rule from the concept of chemical potential. Application of Phase rule to three components system. Principle of triangular diagram: Plots for a mixture of three liquids consisting of one, two and three pairs of partially miscible liquids. Thermodynamics of irreversible processes with simple examples. Uncompensated heat and its physical significance. Entropy production- rate of entropy production, entropy production in chemical reactions. The principle of microscopic reversibility, the Onsager reciprocal relations- Validity and Verification. Thermal osmosis, Thermoelectric phenomena- Electro kinetic and thermo mechanical effects. Application of irreversible thermodynamics to biological and non-linear systems. UNIT-III Quantum Chemistry Inadequacy of classical mechanics, Black body radiation, Planck’s quantum theory, Photoelectric effect. Bohr’s theory of hydrogen atom :Hydrogen spectra, wave particle duality – uncertainty principle. Operators- Linear, differential, Laplacian, Hermitian and Hamiltonian operators angular momentum operator. Eigen functions and Eigen values. commutation relations, related theorems, simultaneous measurement of several properties : evaluation of commutators such as [(x , Px) and (Lx, Ly)] and their significance. Commutation relations, related theorems. Time-dependent and time-independent Schrödinger wave equations – Postulates of quantum mechanics. UNIT-IV Statistical thermodynamics Concept of thermodynamics and mathematical probabilities – Micro and macro state - phase space – Maxwell – Boltzmann, Bose – Einstein statistics and Fermi – Dirac statistics – comparison and applications – modes of contribution to energy. Partition functions. Separation of partition functions. Translational, rotational, vibrational and electronic partition functions. Interpretation of partition function- relation between partition function and Thermodynamic properties: Internal energy, entropy, enthalpy, Helmholtz function, pressure, Gibbs function, residual entropy, equilibrium constant, average energies. Equipartition theorem. Statistical approach to Heat capacity of mono and diatomic gases. Heat capacity of solids- Einstein and Debye models. UNIT-V: MOLECULAR SPECTROSCOPY Introduction and Rotational Spectroscopy Electromagnetic radiation: quantization of energy; rotational, vibrational, and electronic energy levels and transitions in molecules; regions and representation of spectra. Resolution and intensity of spectral transition: signal-to-noise ratio; width of spectral lines- collision broadening, Doppler broadening, Heisenberg uncertainty principle; intensity of spectral lines-selection rules and transition probability, transition moment integral, Einstein absorption and emission coefficients, Boltzmann distribution. Enhancing sensitivity of spectral lines: Fourier Transform (FT) and computer averaging techniques (CAT). Diatomic molecules as rigid rotors: rotational energy levels, intensity of spectral lines, select ion rules, effect of isotopic substitution. Diatomic molecules as non-rigid rotors: rotational transitions, centrifugal distortion constant; rotational spectra of linear and symmetric top polyatomic molecules. INORGANIC CHEMISTRY PRACTICAL - I (Semester - I) Sub. Code: PCHL12 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-1/Core -5/Cpr-2/ I. Qualitative analysis of inorganic mixtures containing two familiar and two less familiar cations: Pb, Cu, Bi, Cd, Sb, Zn, Co, Ni, Mn, Ca, Ba, Sr, W, Tl, Te, Se, Mo, Ce, Th, Zr, V, U, Ti and Li. REFERENCES 1. G. Svehla, Vogel's qualitative inorganic analysis, 7th Edition, Pearson Education India, 2008. 2. V. Ramanujan, Inorganic Semi-micro Qualitative Analysis, 3rd Edition., National Publishing Company, Chennai, 1990. PHYSICAL CHEMISTRY PRACTICAL-I (Semester - I) Sub Code:PCHL13 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-1/Core -6/Cpr-3/ Objective: To learn the Principles of Conductometric Titrations. To study the Principles of Heat of solution. To understand the Kinetics of second order reactions I. Conductometry Conductometric Titrations a. Estimation of HCl and AcOH in a mixture b. Estimation of NH4Cl and HCl in a mixture c. Conductometry- solubility product of sparingly soluble silver salts. II. Thermometry a. Determination of Solution enthalpy of i. oxalic acid-water ii. ammonium oxalate-water iii. Potassium dichromate-water III. Kinetics - Determination of rate of saponification of ester by conductance measurements. *************** ELECTIVE – I ADVANCED TOPICS IN CHEMISTRY – I (Semester - I) Sub Code:PCHE11 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-1/Elec.-1/ Objective: To understand the concept of green and nano chemistry, applied electro- chemistry analytical technique and industrial chemistry. Unit – I : Green Chemistry Need of green Chemistry – Anastas twelve principles of green Chemistry – Concept of atom economy – Green Reactions – Microwave assisted reactions – Superiority of microwave exposure over thermal reactions – Functional groups – Transportation – Condensation reactions – Oxidation and reduction reactions. Unit – I : Nano Chemistry Definition and terminology of Nano particles and Nano structural materials – Synthesis of Nano particles by Physical approaches (Laser ablation, evaporation and sputtering) and Chemical approaches (reduction of metal ions by Citrate and borohydride, Polyol synthesis) green synthesis – Optical and electronic properties of Nano materials. Unit – III : Applied electro Chemistry Principles of Corrosion – Definition – Cost of Corrosion – Electro chemical principles of Corrosion – Corrosion monitoring methods - Coupan (weight loss) – electrical resistance – gasometric – Potentiodynamic polarisation – impedance – hydrogen permeation – Corrosion inhibition – definition – Classification of inhibitors based on electrode process – mechanism of inhibitor action in acidic medium. Unit – IV : Analytical Chemistry Principle and Techniques of GC – MS, HPLC, cyclic voltammetry, Coulometry and Amprometry. Theoretical and practical aspects of Colorimetry analysis - Flame emission and Atomic absorption spectroscopy - Advantages of atomic absorption spectrometry over flame photometry. Unit – V : Industrial Chemistry Nuclear fuels for various types of Nuclear reactors – Hydrogen as fuel in the future, Hydrogen storage materials – Solar energy – fuel from Sun light – Splitting of water – Hydrogen from Sun light – Hydrogen economy – Fuel cells – batteries – Photovoltaics – Stealing the Sun. Nitrenes: Generation, stability, reaction of nitrenes- Mechanism of rearranegements through Nitrene intermediate: Schmidt, Hoffmann, Beckmann rearrangements. Carbanion: Generation, Structure, Stability and reaction of carbanion- Mechanism of rearrangements involving carbanion as intermediate: Steven, Sommelet- Hauser and Favorski rearrangements. Arynes : Generation, Structure, Stability, reactions and trapping of arynes- cine substitution. Unit – IV: ALKALOIDS AND ANTIBIOTICS Alkaloids: Degradation studies – HEM , Emde and Von – Braun – Structural elucidation and synthesis of Quinine, Morphine, Cocaine, Lysergic acid and Atropine. Synthesis of Reserpine and PaPaverine – Biosynthesis of tyrosine, tryptophan. Antibioties: Structure and synthesis of penicillin, cephalosporin – C, chloramphenicol and Streptomycin. Unit – V: VITAMINS AND TERPENOIDS Vitamins: Structural elucidation, synthesis of vitamins – A1, B1 and C - synthesis of vitamins B2, B6 and D. Terpenoids : Structural elucidation, synthesis of α-Pinene, α-Cadinene, Zingiberene, Camphor and sqalene - synthesis of α-Santonin and Gibberelic acid. Bio synthesis of mono and di terpenoids. REFERENCES 1. J. March, ‘Advanced organic chemistry,’ Fourth Edition, John Wiley and sons, New York, 2006. 2. R.T. Morrison and R.N. Boyd, ‘Organic Chemistry’, sixth Edition, Prentice Hall, 1994. 3. I.L. Finar, ‘Organic Chemistry’, volume 2, sixth Edition, Pearson Education Inc., Singapore, 2006. 4. Y.R. Sharma,’Fundamentals of Organic spectroscopy’. 5. P.S. Kalsi, ‘Spectroscopy of organic spectroscopy’, second Edition , New Age International publishers Limited, 1995. 6. Jag Mohan, ‘Organic Analytical Chemistry Theory and Practice, ‘ Narosa Publishing House, 2003. 7. W.Kemp, ‘Organic spectroscopy’, Third Edition, Macmillan, 1994. 8. S.M. Silverstein, G.V.Bassler and T.C. Morril, ‘Spectrometric Identification of organic compounds, sixth Edition, Wiley 2004. 9. D.H.Williams and Ian Fleming, ‘Spectroscopic methods in organic chemistry,’fifth Editon, Tata Mc Graw Hill, 1988. 10. F.W. Wherli and T. Wirthilin, ‘Interpretation of carbon – 13 spectra’, Heyson and sons, London. 11. V.R. Dani, ‘Organic spectroscopy’, Tata Mc Graw Hill, 1995. 12. J.R. Dyer, ‘Application of Absorption spectroscopy, prentice Hall, 1987. 13. Pavia, Lampmann, Kriz and Vyuyan, spectroscopy, cengage learning India Private Ltd., First Indian Reprint,2008. 14. D.H. William and R.D. Bower, ‘Mass spectrometry – principles and Applications,’ I. Howe, Mc Graw Hill. 15. R.M. Silverstein and F.X.Webster, ‘Spectrophotometric Identification of Organic Compounds’ John Wiley and Sons, Ine., Sixth Edition, 1997. 16. F.A. Carey and J.Sundberg,’Advanced Organic chemistry ‘ part A and B, Plenum Press, 2005. 17. Gurdeep Chatwal,’Organic Chemistry of Natural products, Vol I and II, Himalaya Publishing House, Bombay,1992. 18. O.P. Agarwal, ‘Chemistry of Natural Products,’Vol I and II, Goel Publishing House, Meerut, 1984. 19. M. Mukerji, S.P. Singh, and R.P. Kapoor, ‘Organic Chemistry, Vol I and II, Wiley Eastern Ltd., 1985. 20. I.L. Finar, Organic Chemistry , Vol. I. ELBS fifth Edition,2001. 21. R.O.C. Normon, principles of organic synthesis – Chapman and Hall 1994. 22. W. Carruthers, some modern methods & Organic synthesis – Cambridge University Press. 23. E.L. Eliel, stereochemistry of carbon compounds – Mc Craw Hill, 1999. 24. ORD and CD in chemistry and Bio chemistry – Academic press. 25. F.A. Carey, Organic chemistry – Tata Mc Graw Hill, Delhi, 5th edition 2005. 26. Green chemistry by Anastas. 27. Green chemistry by Rashmi and Sanghai. ********** INORGANIC CHEMISTRY – II (Semester – II) Sub Code: PCHM22 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-II/Core-8/ Objectives: • To know the nature of metal-ligand bond and to study various theories of bonding in coordination compounds. • To study the stability, chemical reactions and magnetic properties of coordination compounds. • To study the applications of electronic and infra-red spectroscopic techniques in coordination compounds. • To understand inorganic polymers and to study structures and bonding in metal clusters. Unit – I: BONDING IN COORDINATION COMPOUNDS CFT and LFT: Basic features of CFT and LFT. Splitting of the metal d- orbitals in Td, Oh and square planar symmetries – Jahn-Teller distortion in Oh and Td complexes – Static and dynamic J.T distortions. Application of CFT: Magnetic Properties -Spectral properties - Spectrochemical series – Kinetic properties. CFSE: Calculation of CFSE in Oh and Td complexes - Contribution of CFSC to M-L bond energy, M-L step-wise stability constants, Hydration energies of Mn+ – Lattice energy – Preferred stereochemistry – Site selection of the cations in spinel and inverse spinel and OSSE. MOT: σ-bonding and π-bonding in Oh complexes - Effect of π-bonding on the value of Δ(10Dq). MOT for square planar (16 e-) and Td (18 e-) complexes. Application of MOT to spectrochemical series. Unit – II: STABILITY AND REACTIONS OF COORDINATION COMPOUNDS Stability of complexes: Thermodynamic and kinetic stabilities -stepwise and overall stability constants of the metal complexes – factors affecting stability – chelate and template effects - Determination of stability constants and composition of the complexes: Bjerrum’s method, potentiometric determination, spectrophotometric method, ion-exchange method, polarographic method, continuous variation (Job’s) method. 15. David W. H. Rankin, Norbert W. Mitzel, Carole A. Morrison, Structural Methods in Molecular Inorganic Chemistry, John Wiley & Sons Ltd., 2013. 16. Kazuo Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B: Applications in Coordination, Organometallic, and Bioinorganic Chemistry, John Wiley and Sons, Inc, 6th Ed., 2009. 17. C.N.R.Rao, Chemical Applications of Infrared Spectroscopy, Academic Press, New york, 1963. 18. Roman Boca, Theoretical Foundations of Molecular Magnetism, Elsevier, 1st Edition, 1999. 19. Olivier Kahn, Molecular Magnetism, VCH Publishers, Inc., 1993. 20. Alan Earnshaw, Introduction to Magnetochemistry, Academic Press, 1968. 21. Richard L. Carlin, Magnetochemistry, Springer-Verlag, 1st Edition, 1986. ************ PHYSICAL CHEMISTRY-II (Semester – II) Sub Code: PCHM23 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-II/Core-9/ Objective: To inculcate Knowledge about Quantum mechanics and Statistical Thermodynamics To learn and understand the Principles of Electrochemistry To know about Photochemistry and Radiation chemistry UNIT-I: Quantum Mechanics I Setting up and solving Schrodinger wave equation and arriving solution for Particle in 1D box, Particle in a ring, 3D Rectangular box, 3D cubical box, the harmonic oscillator, the rigid rotator, and the hydrogen atom. Degeneracy and degenerate wave functions, Quantum mechanical tunnelling. Shapes and nodal properties of orbitals – Space quantisation. UNIT-II: Quantum Mechanics II Electron spin, Anti symmetry and Pauli’s exclusion principle – Slater determinantal wave functions. Approximation methods-The Variation theorem; Linear Variation Principle, Perturbation theory. Applications of Variation Method and Perturbation Theory to the Helium atom. Born-Oppenheimer approximation, VB and MO theory, for H2+ molecular ion and H2 molecule problems, Hartree Fock Self consistent field method for Helium atom. Hückel Molecular Orbital Theory and its application to ethylene, butadiene and benzene. UNIT - III Electrochemistry - I Arrhenius theory, Derivation and Validity of Debye-Huckel Theory, Debye-Huckel-Onsager conductance equation, Deviations from Onsager equation. Debye-Falkenhagen effect and Wien effect. Activity of electrolytes, Determination of activity and activity coefficient using Debye-Huckel theory. Debye-Huckel Limiting law, Debye-Huckel-Bronsted equation. Definition and Determination of Transference number. Abnormal transference number. Electrified interfaces-Lipmann equation derivation. Electrical Double Layer, Structure of electrical double layer Helmholtz-Perrin, Guoy-Chapmann and Stern models of electrical double layer- Applications and limitations.Kinetics of electrode reaction-Butler-Volmer equation, Tafel equation. UNIT – IV Electrochemistry - II The Poisson-Boltzmann equation and its solutions. Electrocapillary phenomena-Zeta potential and its applications. Electrophoresis and related phenomena- The electro viscous effect, sedimentation Potential, Electrophoresis. Effect of electrical double layer- Electrocapillarity, Double layer capactance Corrosion and passivation of metals – Pourbaix diagram – Evans diagram – fuel cells – primary and secondary fuel cells – electrodeposition – principle and applications. ` Principles and applications of Polarography–Instrumentation, Interpretation of current voltage curves, tests for reversibility, determination of ‘n’ values (usefulness of Illkovic equation), polarographic maxima, current time curves, Modern developments, Oscillographic polarography, AC polarography – Cyclic Voltammetry, advantages over polarographic techniques – Test of reversibility of electron transfer reactions – Chronopotentiometry – apparatus used, advantages over polarography – controlled potential coulometry. UNIT-V :Photochemistry and Radiation Chemistry: Photochemistry: Introduction. Laws of photochemistry, Quantum yield and its determination. Physical properties of electronically excited molecules: excited state dipole moment, acidity constant and redox Potentials. Photophysical processes in electronically excited molecules: Jablonski diagram – Intersystem system crossing internal conversion, fluorescence, phosphorescence and other deactivation processes. Photosensitisation chemiluminescence and bioluminescence-Stern-Volmer equation and its applications – mechanisms of quenching – electron transfer – energy transfer–experimental techniques in photochemistry –chemical actinometers. Radiation Chemistry Differences between radiation chemistry and photochemistry – sources of high energy radiation and interaction with matter – radiolysis of water, solvated electrons – Definition of G-value- Dosimetry and dosimeters in radiation chemistry- application of radiation chemistry. REFERENCE BOOKS 1. I. N. Levine: Quantum Chemistry, Prentice Hall India, 1994. 2. S. N. Datta: Lecture on Chemical bonding and quantum chemistry, 1998. 3. D. A. McQuairrie: Quantum Chemistry, Oxford University press, Oxford,1982. REFERENCES 1. F.C.Mann and B.C.Saunders, Practical organic chemistry, Fourth edition, ELBS,1970 2. A.I. Vogel, A Text book of Practical organic chemistry. 3. A.I. Vogel, A Text book of Quantitative Organic Analysis,1989. 4. Raj K. Bansal,Laboratory Manual of Organic Chemistry,Second Edition,Wiley Eastern Ltd., 1990 5. Moore, Dalrympk and Rodig, Experimental methods in organic chemistry, 3rd edition, Saunders College publishing, The Oxford Press,1982 6. Bassett et.al., A Text Book of Quantitative Inorganic Analysis,ELBS, 1986 7. Roberts, Gilbert, Reidwald-Wingrove An Introduction to Experimental Organic Chemistry, 1969. INORGANIC CHEMISTRY PRACTICAL - II (Semester - II) Sub Code:PCHL22 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-II/Core -11/Cpr-5/ I. Analysis of Mixture of Cations by Complexometric titrations 1. Estimation of Cu(II) by EDTA titration in the presence of either Pb(II) or Ba(II) (Sepearation of Pb(II) or Ba(II) by precipitation). 2. Estimation of Zn(II) by EDTA titration in the presence of either Pb(II) or Ba(II) (Sepearation of Pb(II) or Ba(II) by precipitation). 3. Estimation of Ca(II) and Pb(II) in a mixture by EDTA titration (Selective titration by control of pH). 4. Estimation of Cr(III) and Fe(III) in a mixture by EDTA titration (Kinetic masking). 5. Estimation of Mg(II) and Mn(II) in a mixture by EDTA titration (Demasking by F−) 6. Estimation of Pb and Sn in Solder alloy by EDTA titration (Demasking by F−). 7. Estimation of Ca(II) ion in an antacid or diet supplement pill by EDTA titration(Substitution titration). II. Photocolorimetric Analysis of Cations Estimation of Fe, Ni, Cr, Mn, Cu and NH4+. (Course work) REFERENCES 1. G.H. Jeffery, J. Bassett, J. Mendham, R.C. Denney, Vogel's Textbook of quantitative chemical analysis, Longman Scientific and Technical, 5th Ed., England, 1989. 2. Douglas A. Skoog, Donald M. West, F. James Holler, Stanley R. Crouch, Fundamentals of Analytical Chemistry, 8th Ed., Brooks/Cole-Thomson Learning, USA, 2004. 3. I.M. Kolthoff, V.A. Stenger, Volumetric Analysis, 2nd Ed., Interscience Publishers, New York, 1947. PHYSICAL CHEMISTRY PRACTICAL-II (Semester - II) Sub. Code: PCHL23 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-II/Core -12/Cpr-6/ Objective: To learn and apply the Principles of Conductometric Titrations. To understand and verify the Principles of Heat of solution. To understand the Partition and distribution of a solute between two immiscible solvents I Conductometric experiments (i) Estimation of K2SO4 using BaCl2 (ii) Estimation of CH3COOH and CH3COOONa in a Buffer solution. (iii) Determination of Dissociation constant of a weak acid (iv) Estimation of NaOH and CH3COONa mixture-link HCl-standard- CH3COONa II Distribution law (i) Distribution of Iodine between two immiscible solvents & Study of the equilibrium constant of the reaction KI+I2 → KI3 (OR) (ii) Distribution of benzoic acid between two immiscible solvents III Thermometry Determination of Solution enthalpy of (i) Benzoic acid-water (ii) Napthalene-Tolune IV Primary Salt Effect- Peroxy disulfate-Iodine reaction V Kinetics – Study of Kinetics of KI-K2S2O8 system. *********** 14.Home page of Prof.Ned Seeman-http://seemanlab4.chem.nyu.edu/ 15.Nano letters –http://pubs.acs.org/journals/nalefd/index.html 16.Nanotation – http://www.acsnanotation.org/. 17.F.W.Bill Meyer, Text book of polymer science, III Edition, John Willey and sons, New York. P.J.Flory. 18.Principles of polymer chemistry, Cornell press (recent edition). V.R. Gowarikar, B.Viswanathan, J. Sridhar. 19.Polymer science- Wiley eastern, 1986. G.S.Misra- Introduction to polymer chemistry, Wiley Eastern Ltd., P.Bahadur, N.V.Sastry. 20.Principles of polymer science, Narosa Publishing House. G.Odian. 21.Principles of Polymerisation,Mc Graw Hill Book company,New York, 1973. 22.A.Rudian, The elements of polymer science and Engineering. Academic press, New York. 1973. 23.I.C.E.H.Brawn, the chemistry of High polymers, Butter worth & co., London, 1948. 24. E. A. Coolins, J. Bares and E. W. Billmeyer, Experiments in Polymer Science, Wiley Interscience, New York, 1973. 25. Advance polymetric materials Editors : Gabriel O. Shonaike & Siuresh G. Advani, CRC Press – 2003 26. Progress in preparation, processing and applications of polyaniline. Progress in polymer Science (2009) 783 – 810 27.Monographs in electrochemistry Conducting Polymers – a new era in electrochemistry Editor : F. Scholz Springer – Verlag, Germany 28.Fundamentals of medicinal chemistry by Gareth Thomas, John Wiley & sons: chichester,2003. 29.Medicinal chemistry: An introductionby Gareth Thomson, Wiley- Interscience, 2nd edition, 2008. 30.An introduction to Medicinal chemistry by graham L.Patric, Oxford university press, USA, 3rd edition, 2005. 31.Wilson and Giswald’s Text book of organic medicinal and pharmaceutical chemistry by john Block and John M.Beale (Eds), Lippincott Williams & Wilkins 11th edition, 2003. 32.The Organic chemistry of Drug Design and Drug Action by Richard B. Silverman, Academic press, 2nd edition, 2004. 33.Designing organic synthesis : The Disconnection Approach by Stuart Warren, Wiley, 2nd edition , 1984. 34.Asymmetric Synthesis by H.B.Kagan, Thieme Medical Publishers,2003. 35.Advanced Organic Chemistry: Part-A and Part-B by Francis A.Carey and Richard B.Sundberg, Springer, 5Th Edition,2007. 36.L.Stryer “Biochemistry” , Freemann and Toppon, 1975. 37.F.S. Gould, Mchanism and structure in organic chemistry, Holt, New York, 1959. 38.R.E.Ireland,Organic Synthesis,Prentice Hall 1969. 39.S.Turner,Design of Organic Synthesis,Elsevier,1976. 40.S.Warren,Designing Organic Synthesis-A programmed Introduction to Synthon approach,Wiley,New York,1978. *********** SECOND YEAR ORGANIC CHEMISTRY – III (SEMESTER-III) Sub Code:PCHM31 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-III/Core-13/ Objectives: 1. To understand the Aliphatic Nucleophilic substitutions, concept of NMR, Mass Spectroscopy. 2. To understand the photochemistry, pericyclic and Hetero cyclic reactions. Unit-I : Aliphatic nucleophilic substitution and Elimination Reactions: Aliphatic nucleophilic substitution : Mechanism of SN1, SN2, SNi, SN1’, SN2’ and SNi’ reactions- Effect of substrate, nucleophile, leaving group and solvent on the rate of substitution- Ambident nucleophile- NGP- Mechanism of esterifications and ester hydrolysis (BAC2 and AAC2 mechanisms only) Elimination reaction: E1, E2 and E1CB mechanisms- Factors influencing elimination reactions- Hofmann and Satyzeff rules- Pyrolytic elimination- Chugaev and cope reactions-competition between substitution and elimination reactions. Unit – II: NMR SPECTROSCOPY 1H-NMR spectroscopy: Basic Principle – number of signals – chemical shift – Factors influencing chemical shift - spin–spin splitting–Proton exchange reactions - classification of spin systems – analysis of AX, AMX and ABX systems – Geminal, Vicinal and long range couplings–NOE in stereochemistry – FTNMR. C-13 spectroscopy: Principle of proton decoupled and OFF- resonance decoupled C-13 spectroscopy - comparison with H1NMR - chemical shifts (aliphatic, olefinic, alkynic, aromatic and carbonyl compounds) 2D NMR spectroscopy: H1–H1COSY, H1–C13 COSY, NOESY, DEPT and INADEQUATE spectra. Unit – III: MASS SPECTROSCOPY Basic Principles– Base peak – molecular ion – nitrogen rule – metastable ions – isotopic peak - daughter ions – Mc–Lafferty rearrangement – RDA – General rules for fragmentation pattern – Fragmentation pattern of simple compounds of hydrocarbons, alcohols, amines, aldehyde, ketone, ether, acids, phenols ,nitro compounds, alicyclic compounds . Alternative electron impact ionization technique– CI, FAB, ESI – MS, MALDI –MS, MALDI-TOF , ICP- MS. 18. Stryer, L., “Biochemistry”, Fifth edition, W.H.Freeman and company, San Francisco, 2002. 19. Jain, J.L., “Fundamentals of Biochemistry”,Fourth edition, S.Chand & Company Limited, New Delhi.2007 20. Bansal, K., “Heterocyclic Chemistry”, Fourth edition, New Age International, New Delhi, 2005. INORGANIC CHEMISTRY - III SEMESTER – III Sub.Code:PCHM32 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-III/Core-14/ Objectives: • To introduce organometallic compounds and to study their catalytic applications in homogeneous and heterogeneous systems. • To study the applications of NMR and EPR techniques in inorganic systems. • To understand the basic principles and applications of thermo and spectro analytical techniques. • To introduce inorganic photochemistry and to study applications in various systems. Unit I – ORGANOMETALLIC CHEMISTRY - I The 18 e− and 16 e− rules and its correlation to stability – Synthesis and structures of metal carbonyls, metal nitrosyls and dinitrogen complexes – Substitution reactions of metal carbonyls - IR spectralapplications – identifications of bridging and terminal CO groups – Stretching mode analysis of metal carbonyls – evidence for M-M bonds. Synthesis, properties and structural features of metal complexes with alkene, alkyne, allyl andarene systems. Metallocenes – synthesis, properties, structure and bonding with particular reference to ferrocene and berryllocene – covalent versus ionic bonding in beryllocene. Template synthesis of macrocyclic ligands. Unit II – ORGANOMETALLIC CHEMISTRY - II Organometallic compounds as catalysts and the requirements: Agostic interaction – Oxidative addition and reductive elimination - insertion and elimination reactions – nucleophilic and electrophilic attack of coordinating ligands - cyclometallation reactions. Homogeneous catalysis: Wilkinson’s catalyst and hydrogenation reactions, Tolman catalytic loop; hydroformylation (oxo) reaction, Wacker and Monsanto acetic acid processes. Cluster compounds, polymer-supported and phase-transfer catalysis. Heterogeneous catalysis: synthesis gas and water gas shift reactions; Fischer Tropsch process and synthetic gasoline, Ziegler-Natta polymerization and mechanism of stereoregular polymer synthesis. Cyclooligomerisation of acetylenes (Reppe’s or Wilke’s catalyst) – Olefin isomerisation using Ni catalyst – olefin metathesis catalysed by Schröck type carbene. UNIT-III: SPECTRAL METHODS TO THE STUDY OF INORGANIC COMPOUNDS – I NMR SPECTROSCOPY: 31P, 19F and 15N – NMR – applications in structural problems based on number of signals, multiplicity, anisotropy (like H3PO3, H3PO2, [HNi(PPh3)4]+, SF4, TiF4, PF5, HPF2, H2PF3, PF3(NH2)2, P4S3, P4N4Cl6(NHC6H5)2, P3N3(CH3)2Cl4, NF3, NH3 – mer- and fac-Rh(PPh3)3Cl3, fluxional molecules (including organometallic compounds) and study of fluxionality by NMR technique - NMR of paramagnetic molecules - contact shifts. Evaluation of rate constants - monitoring the course of reaction using NMR. EPR spectroscopy: Factors affecting magnitude of g-values - Zero field splitting and Kramers’ degeneracy - Application of EPR in the study of transition metal complexes based on number of signals, multiplicity, anisotropy (bis(salicylaldimine)copper(II), [Cu(bpy)3]2+, [Cu(Phen)Cl2], [(NH3)5Co-O2-Co(NH3)5]5+, Co3(CO)9Se, Co3(CO)9Rh, [CoF6]4-, [CrF6]3-, VO(acac)2, [VO(H2O)6]2+, [Fe(CN)5NO]2−). Applications in predicting the covalent character of M-L bond and Jahn-Teller distortion in Cu(II) complexes. EPR spectroscopy of metallobiomolecules: copper and iron proteins. UNIT – IV: THERMOANALYTICAL AND SPECTROANALYTICAL METHODS Theory and principles of thermogravimetric analysis, differential thermal analysis and differential scanning colorimetry – characteristic features of TGA and DTA curves – factors affecting TGA and DTA curves – complementary nature of TGA and DTA – applications of thermal methods in analytical chemistry – thermometric titrations – the study of minerals and metal compounds. Principle and applications of spectrophotometry, spectrofluorimetry, atomic absorption spectroscopy and atomic emission spectroscopy based on plasma sources. UNIT -V : PHOTOCHEMISTRY OF METAL COMPLEXES Frank Condon and thermally equilibrated excited (THEXI) states – properties of excited states of metal complexes – types of excited states, photophysical processes: bimolecular deactivation and energy transfer, photochemical processes: electron transfer reactions, isomerisation and substitutional processes – Photochemistry of Cr(III) and Co(III) complexes – Photophysical and photochemical properties of [Ru(bpy)3]2+. Applications of inorganic photochemistry: photochemical conversion and storage of solar energy – inorganic photochemistry at semi-conductor electrodes - Catalyzed photoreduction of CO2 and CO – TiO2 as a green photocatalyst in removing air and water pollutants. PHYSICAL CHEMISTRY- III SEMESTER III Sub.Code: PCHM33 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-III/Core-15/ Objective: Learning the concepts of Group Theory To understand the Principles and applications of various spectroscopy UNIT-I: Group Theory-I Symmetry elements and operations. Group Postulates and types of groups. Identification of Point groups of molecules and Schoenflies symbols. Construction of multiplication table for C2v, C3v and C2h. Sub-groups and classes of symmetry operations. Rule of similarity transformations. Matrix representations of symmetry operations. Use of atomic wave functions as bases for point group representations. Reducible and irreducible representations. The Great Orthogonality theorem. Properties of Reducible and irreducible representations. Construction of character tables for C2V, C3V, C4V, C2h, and D2 point groups by using The Great Orthogonality theorem. UNIT-II : Group Theory -II : Standard Reduction Formula, Vibrational modes as bases for group representations-Normal mode analysis for non linear molecules H2O, POCl3, trans-N2F2 and PtCl4. Symmetry selection rules for infrared and Raman spectra. Mutual exclusion principle. Determination of Hybridisation of atomic orbitals in non-linear molecules (CH4, XeF4, and PF5). Electronic spectra of ethylene and formaldehyde molecules. Construction of Projection operators and Molecular orbitals by Symmetry Adapted Linear Combinations. Simplification of HMO calculations using group theory. Calculation of delocalization energy for ethylene, trans-1,3 – butadiene, and benzene systems. UNIT – III: Nuclear Magnetic Resonance Spectroscopy Theory of Proton NMR spectroscopy, Chemical shift and its measurement, Factors influencing chemical shift, Solvents used in NMR, solvents shift-concentration and temperature effects-hydrogen bonding. Theory of Spin-spin splitting-Magnitude of coupling- coupling constants, J, First-order spectra of complex systems, chemical and magnetic equivalence in NMR, Proton exchange reactions, Factors influencing coupling constant, J. Theory and Principle of 13C, 19F, 31P NMR-Range of chemical shift values, spectra of typical examples. FT NMR-FIDs. Theory of Spin-spin splitting and double irradiation, InterNuclear Double Resonance (INDOR) and Selective Population Inversion (SPI), Nuclear Overhauser Effect (NOE), 2D NMR-shift correlation spectra-COSY, Magnetic Resonance Imaging (MRI). UNIT-IV: NQR and EPR spectroscopy Electron paramagnetic resonance spectroscopy: theory of EPR spectroscopy, presentation of the spectrum, nuclear hyperfine splitting in isotropic systems. EPR spectra of anisotropic systems: anisotropy in g-value, causes of an isotropy, anisotropy in hyperfine coupling. Double resonance in ESR, Zero field splitting and Kramers’ degeneracy. Theory and Principle of NQR spectroscopy-Nature of electric field gradient, Energy levels and selection rules, Interaction of electric quadrupole with electromagnetic radiation, nuclear orientations, the asymmetry parameter, quadrupole transitions in spherical, axially symmetric fields and not axially symmetric fields. Applications of NQR spectra. UNIT-V: Electronic Spectroscopy, Mossbauer Spectroscopy and Mass Spectrometry Electronic Spectroscopy-Electronic Spectrum of diatomic molecules-Born-Oppenheimer approximation, Progressions, Franck-Condon Principle, Dissociation Energy and dissociation products, Rotational Fine structure of Electronic-Vibration Transitions, The Fortrat diagram, Predissociation, Electronic states of atoms, Electron orbitals in diatomic molecules, Electronic states of diatomic molecules, Potential energy curves for Electronic states of diatomic molecules. Photoelectron Spectroscopy-Basic Principles, Ultra-Violet Photoelectron Spectroscopy, X-ray Photoelectron Spectroscopy, Chemical information from Photoelectron Spectroscopy. Mössbauer spectra: Theory and Principle of Mössbauer spectra, isomer shift, quadrupole interactions, magnetic hyperfine interaction, Doppler shift, recoil energy, experimental technique-sources, absorber, calibration, Chemical applications. Mass spectrometry: Operation and representation of spectra. Effect of combination of high energy electron with a molecule. Finger print application and the interaction of mass spectra, Effect of isotopes on the appearance of a mass spectrum, Molecular weight determinations. REFERENCE BOOKS 1. Introductory Group Theory For Chemists- George Davidson 2. F. Albert Cotton, Chemical Applications of Group Theory, Third Edition John Wiley & Sons, Singapore 2003. 3. V. Ramakrishnan and M. S. Gopinathan: Group Theory in chemistry, Vishal Publication, 1986. 4. Robert L. Carter, Molecular Symmetry and Group Theory John Wiley and Sons, Inc., New York, 1998. 5. R.L. Flurry, Jr, Symmetry Groups – Prentice Hall, New Jersy 1980. 6. Group Theory and its applications to Chemistry by K. V. Raman 7. Group Theory and Spectroscopy by K. Veera Reddy 8. Group Theory and its Chemical applications by B.K. Battacharya 9. C.N. Banwell and E. M. McCash, Fundamentals of Molecular Spectroscopy, 4th ed., Tata McGraw Hill, New Delhi, 2000. 10. K. V. Raman, R. Gopalan and P. S. Raghavan, Molecular Spectroscopy, Thomson and Vijay Nicole, Singapore, 2004. 11. I.N. Levine, Molecular Spectroscopy, John Wiley & Sons, New York, 1974. 12. Organic spectroscopy, William Kemp, Third Edition. 13. Spectroscopy (Atomic and Molecular) Gurdeep R. Chatwal and Sham K. Anand, Himalaya Publishing House 14. R. S. Drago, PhysicaI Methods in Chemistry; Saunders: Philadelphia, 1977. 15. J. A. Weil, J. R. Bolton and J. E. Wertz, Electron Paramagnetic Resonance; Wiley Interscience: 1994. 16. Introduction to Molecular spectroscopy, G.M. Barrow, McGraw-Hill international editions. 17. R.M.Silverstein and F. X. Webster, Spectroscopic Identification of Organic Compounds, 6th ed., John Wiley & Sons, New York, 2003. Organic Chemistry Practical – III Semester- III Sub Code:PCHL31 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-III/Core-17 /Cpr-7/ Estimations, two stage preparations and Spectral interpretation have been included as the practical components. Microscale preparations are recommended for the simple reason, they are both economic-friendly and eco-friendly A.List of Estimations 1.Ethylmethylketone 2.Acetone 3. Saponification value of an oil 4.Determination of Percentage purity in an unsaturated acid. 5. Estimation of hydroxyl group B. List of Two stage preparations 1.Benzaldehyde Benzoic acid m-nitro benzoic acid 2. Acetanilide p-acetanilide p-Bromoaniline 3.Methyl benzoate m-nitro methyl benzoate m-nitro benzoic acid 4. Acetanilide p-nitro acetanilide p - nitroaniline 5. Benzophenone Benzo phenone oxime Benzanilide Students are expected to submit the recrystallised samples of the final products, at the time of practical examination, for evaluation by the examiners. C. For Class work Only : 1. Download the following spectra from internet and give interpretation. Differentiate the following pair by H1NMR spectra (a) Maleic acid and Fumaric acid. (b) Aqueous ethyl alcohol and Pure ethyl alcohol. (c) Dimethyl Ether and Aqueous ethyl alcohol. Interprete the following C-13 NMR Spectra. (a)OFF- Resonance decoupled C-13 spectrum of menthol. (b) DEPT spectrum of isopentyl acetate. (c) INADEQUATE spectrum of 2- butanone. Interprete the mass spectrum of anisole and benzoic acid. N.B: 1.Section -C is course work only. 2. It is for the purpose of internal assessment only. REFERENCES 1.F.C.Mann and B.C.Saunders, Practical organic chemistry, Fourth edition, ELBS,1970 2.A.I. Vogel, A Text book of Practical organic chemistry. 3. A.I. Vogel, A Text book of Quantitative Organic Analysis,1989. 4. Raj K. Bansal,Laboratory Manual of Organic Chemistry,Second Edition,Wiley Eastern Ltd., 1990 5.Moore, Dalrympk and Rodig, Experimental methods in organic chemistry, 3rd edition, Saunders College publishing, The Oxford Press,1982 6.Bassett et.al., A Text Book of Quantitative Inorganic Analysis,ELBS, 1986 7.Roberts, Gilbert, Reidwald-Wingrove An Introduction to Experimental Organic Chemistry, 1969. 8.V.K.Srivastava and K.K.Srivastava, Introduction to Chromatography-Theory and Practice, S.Chand & Co., 1987. INORGANIC CHEMISTRY PRACTICAL – III Semester - III Sub.Code: PCHL32 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-III/Core-18 /Cpr-8/ I. Quantitative estimation of a mixture containing two metal ions (Volumetric and Gravimetric Estimations). 1. Estimation of mixture of Cu2+ and Ni2+ ions. 2. Estimation of mixture of Cu2+and Zn2+ ions. 3. Estimation of mixture of Fe2+and Cu2+ ions. 4. Estimation of mixture of Fe2+ and Ni2+ ions. 5. Estimation of mixture of Ca2+ and Mg2+ions. 6. Estimation of mixture of Ca2+ and Ba2+ ions. II. Analysis of ores and alloys (course work). III. One day visit to Industry/Research Institution and submission of a minor report. REFERENCES 1. G.H. Jeffery, J. Bassett, J. Mendham and R.C. Denney, Vogel’s Textbook of Quantitative Chemical Analysis, Revised 5th edition, ELBS, 1989. 2. Mounir A. Malati, Experimental Inorganic/Physical Chemistry - An Investigative, Integrated Approach to Practical Project Work, Woodhead Publishing Limited, Reprint 2010. palladium(Still coupling, Suzuki Coupling, Heck and Negishi reactions) samarium(SmI2), ruthenium(RuO2,Ru-Binap Complex), platinum(PtO2, Adam’s Catalyst) reagents in organic synthesis. Unit-V : Steroid Classification- structural elucidation of cholesterol, irradiated products of ergosterol. Conversion of cholesterol to androsterone, progesterone, testosterone, 5α- and 5 β-cholanic acid. Conversion of Oestrone to Oestriol, Oestrodiol and vice-versa. Conformational structure of cholestane and Coprostane. General study of Bile acids and Prostoglandins. REFERENCES 1.J.March, ‘Advanced organic chemistry’, Fourth Edition, John Wiley and Sons, Newyork, 2006. 2. R.T. Morrison and R.N. Boyd,’Organic Chemistry’ sixth Edition, Prentice Hall, 1994 3. Michael B. Smith, ‘Organic Synthesis,’ Mc Graw Hill international Edition , 1994 4. R.O.C. Norman, Principles of organic synthesis- Chapman and hall, London. 5. Carrutherus , W., “ Some Modern Methods in Organic Synthesis”, Third edition, Cambridge University Press, New York, 1997 6. P. Sykes, ‘A Guide book to mechanism in organic chemistry’,Orient Longman. 7. J.M.Swan and D.St.C.Black, Organometallics in Organic synthesis 8. Gurdeep R. Chatwal, ‘Reaction mechanism and Reagents in organic chemistry’, Himalaya publishing House, Bombay 1992 9. E.L. Eliel, stereochemistry of carbon compounds – Mc Craw Hill, 1999 10. Gurdeep R. Chatwal, ‘Reaction mechanism and Reagents in organic chemistry’, Himalaya publishing House, Bombay 1992. 11.R.C.Mehrota and A.Singh, Organometallic chemistry-a unified approach-Wiley Eastern. 12. F.A. Carey and R.A Sundberg, ‘Advanced Organic Chemistry’ (part A and B). 13. B.M.Trost & I Fleming. Comprehensive Organic Synthesis. Vols 1-9, Pergamon (1991) 14. I.L. Finar, Organic Chemistry , Vol. II. ELBS 15. L.Fieser and Mary Fieser, Steroids-Reinhold 16.A.L. Lehninger, D.L.Nelson and M.M.Cox-Principles of Biochemistry-Worth Publishers Inc. USA,1993 17. F.A Carey,’Organic Chemistry, Tata Mc Graw Hill, fifth reprint, 2005. 18. A.Burger, Medicinal chemistry-Acdemic press. 19.R.E. Ireland,Organic Synthesis-Prentice Hall of India (P)Ltd. 20.S.Warren,A Programmed Synthon approach-John Wiley & Sons. 21.R.K.Mackie & D.M.Smith, Guide book t organic syntheisi-ELBS. 22.Progress in chemistry of Natural products, Vol.19,1961, JCSC Lon., 869, 1952 23.Michael B.Smith, Organic Synthesis-McGraw Hill International Edition. 24.Paula Yurkanis Bruice, Organic Chemistry-Third Edition-Pearson Education Asia 25.Seyhan Ege, Irganic chemistry-A.I.T.B.S.Publishers & Distributors (Regd.) Delhi INORGANIC CHEMISTRY- IV SEMESTER – IV Sub.Code :PCHM42 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-IV/Core-21/ Objectives: • To study the applications of Mossbauer, photoelectron and nuclear quadrupole resonance spectroscopic techniques in inorganic systems. • To study the applications of ORD and CD to determine absolute configuration of chelate complexes. • To introduce bioinorganic chemistry and to study role of metalloporphrins and metalloenzymes in various biological processes. • To give an insight into material science. UNIT - I : SPECTRAL METHODS TO THE STUDY OF INORGANIC COMPOUNDS – II Mossbauer spectroscopy : Principle – isomer shift (IS) – splitting of resonance lines: quadrupole splitting and magnetic hyperfine splitting. Applications: MB spectra of iron compounds/complexes – structural elucidation, π- bonding effect, determination of high spin and low spin, spin state crossover and cis–trans isomers – nature of the complexes – mixed valence complexes. Tin compounds: MB spectra of Sn(II) and Sn(IV) compounds, oxidation states of Sn in its different compounds. Applications in bioinorganic chemistry: oxy and deoxy- hemerythrin - catalase, peroxidases, Fe-S protein systems. ORD AND CD - Optical isomerism in octahedral complexes – absolute configuration of chelate complexes from ORD and CD. UNIT - II: SPECTRAL METHODS TO THE STUDY OF INORGANIC COMPOUNDS – III Photo electron spectroscopy: Theory – types of PES –origin of fine structures – adiabatic and vertical transitions – PE spectra of homonuclear diatomic molecules (N2, O2) – hetero nuclear diatomic molecule (CO) – polyatomic molecules (H2O, CO2, CH4, NH3). Evaluation of vibrational constant – Koopman’s theorem – application and limitation of the theorem. XPS (ESCA): structure of N3− ion, CCl3CH3, N (1s) spectrum of [Co(en)2(NO)2]NO3, C(1s) spectrum of C2H5COOCF3. Shake-up and shake-off processes – Structural and bonding information in metal carbonyls – Auger electron spectroscopy. NQR spectroscopy: Applications – fingerprint technique. Investigating the electronic structure of molecules – information about EFG of nuclei – ionic character and hybridization PHYSICAL CHEMISTRY- IV SEMESTER – IV Sub.Code :PCHM43 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-IV/Core-22/ Objective: To understand the Principles and applications of Vibrational and Raman spectroscopy To obtain Knowledge Fast reaction study To learn the Theories and applications of Kinetics To Know the Principles of Surface Chemistry and Catalysis UNIT - I: Vibrational Spectroscopy Vibrating diatomic molecule: Energy of diatomic molecules as simple harmonic oscillator- energy levels, vibrational transitions, selection rules; anharmonic oscillator-energy levels, selection rules, vibrational transitions. Diatomic vibrating rotator: Born-Oppenheimer approximation, vibration-rotation spectra, selection rules, P, Q, R branches. Vibrations of polyatomic molecules: symmetry and fundamental vibrations, normal modes of vibration, overtones, combination, difference bands; influence of rotations on the spectra of polyatomic molecules-parallel and perpendicular vibrations in linear and symmetric top molecules. UNIT-II: Raman Spectroscopy Lasers: Nature of stimulated emission-coherence and monochromaticity, population inversion, cavity and mode characteristics, Q-switching, mode locking; types of lasers-solid- state, gas, chemical, and dye lasers. Raman Effect: Quantum theory of Raman effect, Classical theory of Raman effect, Pure rotational Raman spectra- linear molecules, symmetric top and spherical top molecules, Vibrational Raman spectra-symmetry and Raman active vibrations, rule of mutual exclusion; Overtone and combination vibrations, Vibrational Raman spectra, Rotational Fine structure. Polarisation of light and Raman effect-The nature of Polarized effect, Vibrations of spherical top molecules and other types of molecules. Structure determination from Raman and Infra- red spectroscopy, Applications of IR and Raman spectroscopy: skeletal and group vibrations, finger printing and absorption frequencies of functional groups for inorganic and organic compounds. Techniques and instrumentation, Near-Infra-red FT-Raman spectroscopy. UNIT-III: Chemical Kinetics I Reactions in Flow systems-Techniques for very fast reactions-Stopped-Flow method, Relaxation methods, Shock-Tube methods, Temperature, Pressure, electric field and magnetic field jump methods, Flash photolysis and pulse radiolysis. NMR and ESR methods of studying fast reactions. Collision theory. Potential Energy surfaces-energy of activation. Statistical mechanics and chemical equilibrium- Derivations of rate equations Symmetry numbers and statistical factors. Application of ARRT to Reaction between atoms and reaction between molecules. Thermodynamic Formulation of conventional transition state theory, Limitations of transition state theory. Vibrational transition state theory, Quantum mechanical transition state theory , Microscopic reversibility. Unimolecular reactions- Lindemann-Christiansen hypothesis, Hinshelwood, RRK, RRKM and Slater theories. UNIT-IV: Chemical Kinetics II Elementary reactions in solution-Solvent effects on reaction rates, Factors determining reaction rates in solution- collisions in solution, Transition State Theory, Influence of internal pressure, influence of salvation. Reaction between ions- Influence of solvent dielectric constant, Pre-exponential Factors, Single-Sphere Activated Complex, Influence of ionic strength. Influence of Hydrostatic Pressure-Van’t Hoff’s equation and volumes of activation. Substituent and correlation effects-Hammett equation, Compensation effect. Composite reactions-Types of composite mechanism, Rate equations for composite mechanisms, Simultaneous and consecutive reactions, Steady –State Treatment, Kinetics of H2-Cl2 and H2-Br2 reactions, Formation of Phosgene-decomposition of O3 and N2O5. Rice- Herzfeld mechanism, Explosive reactions: H2-O2 reaction. UNIT-V: Surface Chemistry & Catalysis Introduction: Adsorption- Physisorption and chemisorptions. Adsorption isotherms: Freundlich, Langmuir, BET and Gibbs adsorption isotherms. Surface area dertermination. ARRT to surface reactions. Micelles: Micelles and reverse micelles- microemulsion- solubilisation. Catalysis: Homogeneous catalysis- acid-base catalysis- Van’t Hoff and Arrehenius complexes for Protropic and Protolytic mechanisms. Bronsted catalysis law- Hammett acidity function. Heterogeneous catalysis. Chemical reactions on solid surfaces. Enzyme catalysis: Michaelis-Menton Kinetics- Rate of enzyme catalyzed reaction- effect of substrate concentration, pH and temperature on enzyme catalyzed reactions. REFERENCE BOOKS 1. C.N. Banwell and E. M. McCash, Fundamentals of Molecular Spectroscopy, 4th ed., Tata McGraw Hill, New Delhi, 2000. 2. K. V. Raman, R. Gopalan and P. S. Raghavan, Molecular Spectroscopy, Thomson and Vijay Nicole, Singapore, 2004. 3. Spectroscopy, Volume-3, B.P. Straughan and S.Walker. 4. I.N. Levine, Molecular Spectroscopy, John Wiley & Sons, New York, 1974. 5. Organic spectroscopy, William Kemp, Third Edition. 6. Spectroscopy (Atomic and Molecular) Gurdeep R. Chatwal and Sham K. Anand, Himalaya Publishing House 7. R. S. Drago, PhysicaI Methods in Chemistry; Saunders: Philadelphia, 1977. 8. Introduction to Molecular spectroscopy, G.M. Barrow, McGraw-Hill international editions. 9. Chemical Kinetics and Dynamics; Jeffrey I Steinfeld, Joseph S. Francisco and William L. Hase. Prentice Hall, 2nd edition, 1998. 10. Laidler, K. J.; “Chemical Kinetics", 3rd Edition 1997 , Benjamin-Cummings. Indian reprint - Pearson 2009. 11. R.G.Frost and Pearson, Kinetics and Mechanism, Wiley, New York,1961. 12. W.J.Moore and R.G.Pearson, Kinetics and Mechanism,1981. 13. C.Capellos and B.J.J.Bielski,Kinetics Systems,Wisely Inter Science,New York, 1972. 14. Ambur and G.G.Hammes, Chemical Kinetics, Principles and Selected Topics, McGraw Hill, New York, 1968. 15. G.M.Harris, Chemical Kinetics, D.C.Heat And Co.,1966. 16. G. L. Agarawal, Basic Chemical Kinetics, Tata McGraw Hill, 1990. 17. G. D. Billing & K. V. Mikkelson, Molecular Dynamics and Chemical Kinetics, John Wiley, 1996. 18. A.W. Adamson, A.P. Gast, Physical chemistry of surfaces, Wiley, 1997. 19. H.-J. Butt, K. Graf, M. Kappl, Physics and Chemistry of Interfaces, Wiley-VCH, 2006. 20. D.K. Chakrabarty and B. Viswanathan, Heterogeneous Catalysis, New Age, 2008. 21. H. Kuhn, H.-D. Forsterling, D.H. Waldeck, Principles of Physical Chemistry, Wiley, 2009. 5.Moore, Dalrympk and Rodig, Experimental methods in organic chemistry, 3rd edition, Saunders College publishing, The Oxford Press,1982 6.Bassett et.al., A Text Book of Quantitative Inorganic Analysis,ELBS, 1986 7.Roberts, Gilbert, Reidwald-Wingrove An Introduction to Experimental Organic Chemistry, 1969. 8.V.K.Srivastava and K.K.Srivastava, Introduction to Chromatography-Theory and Practice, S.Chand & Co., 1987. INORGANIC CHEMISTRY PRACTICAL – IV Semester - IV Sub.Code :PCHL42 2017-18/ MSU/46th SCAA/ Affiliated coll./PG/M.Sc.(Chemistry)/Sem.-IV/Core -24/Cpr-11/ I. Preparation of inorganic complexes and quantitative estimation by volumetric or instrumental methods . 1. Preparation, and analysis of potassium trisoxalatochromate(III) trihydrate K3[Cr(C2O4)3].3H2O 2. Preparation and analysis of potassium hexathiocyanatochromate(III) tetrahydrate K3[Cr(SCN)6].4H2O 3. Preparation and analysispotassium trisoxalatomanganate(III) trihydrate K3[Mn(C2O4)3].3H2O 4. Preparationand analysis of potassium trisoxalatoferrate(III) trihydrate K3[Fe(C2O4)3].3H2O 5. Preparation and analysis of potassium trisoxalatocobaltate(III) trihydrate, K3[Co(C2O4)3].3H2O 6. Preparation and analysishexamminecobalt(III) Chloride, [Co(NH3)6]Cl3 7. Preparation and analysis of chloropentaamminecobalt(III) chloride, [Co(NH3)5Cl]Cl2 8. Preparation and analysis of trinitrotriamminecobalt(III), [Co(NH3)3(NO2)3] 9. Preparation and analysis of trans-dichlorobis(diaminoethane)cobalt(III) chloride, trans-[Co(en)2Cl2]Cl 10. Preparation and analysis of (NH4)2[VO(C2O4)2].2H2O II. Characterisation of metal complexes prepared during the practicals by UV and IR spectral techniques (Course work). III. Study of linkage isomerism in pentaamminenitritocobalt(III) chloride, and pentaamminenitrocobalt(III) chloride using IR (Course work). REFERENCES 1. Mounir A. Malati, Experimental Inorganic/Physical Chemistry - An Investigative, Integrated Approach to Practical Project Work, Woodhead Publishing Limited, Reprint 2010. 2. W. G. Palmer, Experimental Inorganic Chemistry, Cambridge University Press, Reprint 1970. 3. George Brauer, Handbook of preparative inorganic chemistry, 2nd Edition, Academic Press, 1963. 4. G.H. Jeffery, J. Bassett, J. Mendham and R.C. Denney, Vogel’s Textbook of Quantitative Chemical Analysis, Revised 5th edition, ELBS, 1989. 5. Geoffrey Pass, Haydn Sutcliffe, Practical Inorganic Chemistry - Preparations, reactions and instrumental methods, Springer 1974.