KARANATAKA STATE OPEN UNIVERSITY

M.SC CHEMISTRY

SYLLABUS

Regulations Governing M.SC Chemistry 1. Title of the Program: M.SC CHEMISTRY 2. Duration of the Program: 2 Year 3. Nature of the Program: Semester System 4. Eligibility Conditions: B.Sc (Chemistry / Bio-Chemistry) 5. Allocation of Credits Total -74- Credits 6. Evaluation System : The distribution of marks for evaluation in each subject shall be as follows Theory Subjects : Internal assessment Term End University Examination Practicals : Internal assessment ( for each practical) Term End University Examination Project : Internal Assessment University Examination 50 marks 150 marks 20 marks 80 marks 20 marks 80 marks

Minimum for pass :32 marks per course in theory and aggregate 40% including assessment Course exemption : 40% marks and above in each course

IYEAR-I Semester Subject Code INT EXT TOTAL

Course Title

Credits 4 3 4 4

MARKS MARKS MARKS 20 20 20 20 20 20 20 20 20 80 80 80 80 80 80 80 80 80 100 100 100 100 100 100 100 100 100

1.1 Organic Chemistry-I 1.2 Inorganic Chemistry-I 1.3 Physical Chemistry 1.4 Environmental Chemistry 1.5 Laboratory-Inorganic Chemistry I SEMESTER II SEMESTER III SEMESTER IV SEMESTER

4 3 4 4

2.1 Organic Chemistry-II 2.2 Inorganic Chemistry-II 2.3 Physical Chemistry-II 2.4 Bio-organic Bio-Inorganic, and Bio-physical Chemistry Laboratory-Inorganic Chemistry

2.5

4 4 4 4 3 4

20 20 20 20 20 20 20 20 20 50

80 80 80 80 80 80 80 80 80 150

100 100 100 100 100 100 100 100 100 200

3.1 Organic Chemistry-III 3.2 Inorganic Chemistry-III 3.3 Physical Chemistry-III 3.4 Computational Chemistry 3.5 Laboratory-Physical Chemistry 4.1 Principles of Analytical Chemistry

4 4 4

4.2 Surface Chemistry 4.3 Chemistry of materials 4.4 Project

SUBJECT CODE: 1.1 SUBJECT: ORGANIC CHEMISTRY - I UNIT I Mechanism of electron displacement in Organic molecules: Effect of structures in the dissociation constant of acids bases-EDA complexes crown ether complexes inclusion compounds Quantitative treatment of the effect of structure on reactivity the hemmett relationship significance of reaction of reaction and substituent constants application of the Hammett equation Limitation and deviations. Introduction to reaction mechanism reactive intermediates free radicals carbenes nitrenes carbanios carbocations Formation and stability of these species. Aromatic electrophillic disubstitition partial rate factors. Kinetic and non kinetic methods of, determining organic reaction mechanism. UNIT II Stereochemistry: Study of symmetry of molecules-as symmetric and

dissymmetric molecules-concept of chirality and optical isomerism-molecules with more than one chiral centre Axial chairality in allenes, biphenyls and spiranes. R, S notation of the above molecules, stereocpecificity and steroselectivity, asymmetrics synthesis Crams rule Prelogs rule. E, Z nomenclature of geometrical isomers. Conformational Analysis: Conformations of cyclic systems up to sixmembered conformational analysis of mono-and disubstituted cyclohexanes Effect of conformation of decalins per hydro phenentherenes. UNIT III Alkaloids: Structure, synthesis and stereochemistry of the following alkaloids. Quinine, Norphine, streptomycin and Tetracyclin.

Antibiotics: Structure and synthesis of the following: cephalosporin C, penicillin, streptomycin and Tetracyclin.

Chloramphenicol,

UNIT IV Aromatic: Benzenoid and non-benezenoid aromatic compounds-Hackles rule concept of homoaromaticity and anti-aromaticity systems with 2,4,6,8, and 10 electrons. Annulenes Fulvene, azulene and tropolones. Heterocyclic Compounds: Synthesis and reactions of sydnones, carbazole and imidadole structure elucidation of flavones, quercetin, cyanic, caffeine, theobromine and theophylline. UNIT V Aliphatic and aromatic nuclecophillic substitution : SN1and SN2

mechanisms effect of substrate structure, nucleophile, leaving group and the solvent on nucleophillic substitution-symphoria NGP due to n and electrons SN1, SN2, SNi and SN I; mechanisims. Eliminations: E1,E2, and E1,CB mechanism effect of the subsrate structure, base solvent and the leaving group on elimination Hofmann, saytzess and Bredts rules. Aromatic nucleophillic, substitution benzyne mechanism von Richter rearrangement. Mechanism of addition to multiple bonds: Stereo chemical factors in the addition of the following to carbon carbon double bonds, hydrogen halogens, hydrogen halide hydro oration hydroxylation. Mechanism of mannich reaction, Claisen ester condensation, Dieckman condensation, sobbed

condensation Darzens reaction, Refomatsky reaction, Witting and Grignard reactions Stocks enamine reaction Michael addition. REFERENCE BOOKS:

UNIT I 1. The Modern structure Theory of Organic Chemistry L.N.Fergusar-Prentc Hall. 2. Mechanism and Structure in Organic Chemistry E.S Gould-Henry Holt & Co 3. Mechanism and Theory in Organic Chemistry-T.H.Lowry and K.S.Richarson. 4. Organic Chemistry-S.Pine Mc. Graw Hill, kogakusha LTD. 5. Advanced Organic Chemistry-Jerry March,J.Wiley. 6. Organic Chemistry R.T Morrison and Boyd, Prentice Hall. 7. A Guide book to Mechanism in Organic chemistry. P.Sykes- Orient Longman. 8. Organic Chemistry Vol.IIl Finar ,ELBS 9. Fundamental of Organic Reaction Mechanism J.M. Harris and C.C Warnser John Wiley & Sons 10. 11. 12. Reaction Mechanism In Organic Chemistry BanSal Advance Organic Chemistry Part A F.A Carey and R.j Sundberg Correlation Analysis In Orgsnic Chemistry- J.Shorter Clarendress. Press, oxford

UNIT II 1. Stereochemistry of carbon compounds- E.L.Eliel, Mc. Graw Hill. 2. Introduction to Stereochemistry K.Miislow Benjamin

3. Stereochemistry V.M Potapov- MIR Publishers. 4. Stereochemistry of Organic Compounds Principle & Application,

D.Nasipuri - Wiley-Eastern LTD 5. Sterochemistry Eastern. 6. Organic Chemistry Vol II ELBS Conformation and Mechanism R.S Kalsi Wiley

UNIT III 1. The Alkaloids-Bentley-Inter Science Publishers. 2. Chemistry of Alkaloids Pelletier 3. The Chemistry of Organic Nature Products O.P AgarwalGoel

Publishing House. 4. Organic Chemistry Vol I.L Finar ELBS 5. Monograph Series as The Alkaloids 6. Medical Chemistry A .Burges- Academoc Press

UNIT IV 1. Aromatic Character and Aromaticity G.M. Badger CamBridge 2. Aromaticity S.J Garelt Hill. 3. Advance Organic Chemistry J.March, Wiley 4. Organic Chemistry Vol. I& II- Finar ,ELBS 5. Chemistry of Heterocyclic compound R.M. Acheson Wiley Eastern. 6. The Chemistry of Organic Natural Products- O.P Agarwal Goel Publishing House.

UNIT V 1. The Mechanism and Theory In Organic Chemistry T.H Lowry and K.S Richardson. 2. Advanced Organic Chemistry J.March, Wiley. 3. Mechanisms and Structure in Organic Chemistry .E.S Gould- Henry Holt & Co, New York. 4. Fundamental of Organic Reaction Mechanisms J.M. harris and C.Warser John Wiley & sons. 5. AGuide Book to Mechanism in Organic Chemistry P.Sykes Orient Longman 6. Reaction Mechanism In Organic Chemistry Bansal 7. Organic Chemistry R.T Morrison &R.N Boyd 8. Stereochemistry of Carbon Compounds- E.L Eliel Mc Graw Hill. 9. Organic Chemistry Vol-IL Finar 10. Advanced Organic Chemistry Part A F.A Corey and R.J sundberg-

Plemum Press

SUBJECT CODE: 1.2 SUBJECT: INORGANIC CHEMISTRY I UNIT I Bonding and Stereochemistry: Electronic Configuration of element

0signification of quantum number- polyelectronic atom- Paulis- Aufbau principle-qualitative treatment of VB and MO theory and bonds hybridisation and resonance- application of VB and MO theory the electro

deficient molecule-boron hydrides and metal alkyls. Bond order Bound energy- bound length- bound polarity-partial ionic character-eletronegativity and different scales of Pauling, mulliken, Aldrich and Rochow and Sanderson Scales- Coversion to Pauling scale- periodicity of

electronegatirity, electron affinity and ionic radius-lattice energy affinity or lattice energy covalent character ionic compounds- different types of electrostatic interaction, hydrogen bounding Stereochemistry, VSEPR,walsh diagrams (tri and penta atomic molecules)
d

bounds Bents rule and

energetic of hybridisation use of Bents rule apicophilicy. UNIT II Solid State Chemistry: Elements of Crystallography- Space lattice Unit cellcrystal systems X-ray diffraction ,Braggs equation Braggs methods-

rotating method and power method of X-ray diffraction Struture of typical Lattices such as calcite Zinc blende, Wurtzite Rutile, Fluorite antifluorite, pervosakite.Crystal defects in solids-line and plane defects non-stoichiometryscjotty and Frenkel defects and colour centers: Solid electrolytes. Free electron and band theory semiconductors- Hall effect Photovoltaic and solar energy conversion superconductivity-high temperature super

conductors- cooper electrons - Meissenner effect and levitation.

UNIT III Nuclear Chemistry: Radioactivity and modes of decay , and y Different types of nuclear reaction with natural and artificial particles Q value, cross section, spellation, fission and fusion. Characteristics of fission reaction, product distribution and for fission of liquid drop model, fissile and fertile isotopes: nuclear fusion and stellar energy. Transmutation of elements and chemical effect on transmutation. Isotopes and their application, radioactive analysis and counting techniques Geiger Muller, Ionisation; proportional and scintillation counter) Radio analytical Methods: Neutron activation analysis-Isotopic dilution methods- Radiometric titrations.

UNIT IV Coordination Chemistry and Magnetism: Bounding in coordination

Compound Nature of metal- ligand bound: VB theory-Electro neutrality principle and back bounding crystal field effects for

octahedral,tetragonal,square planar and tetrahedral symmetries, application of CFT Site preferences; spectrochemical series and nephalauxitic effect :MO theory for octahedral, complexes- pi bounding and MOT;- static and dynamic Jahn-Teller behaviour. Magnetic behaviour-dia, Para, Ferro and antiferro magnetisms: magnetic moment determination by Guoy and Faraday methods; Spain only value and its deviation-Quenching of orbital angular moment a and spin-orbit coupling. Determination of geometry of Co and Ni complexes from magnetic data. Spam Cross over Phenomenon; magnetic properties of lanthanides and actinides.

UNIT V

Metallurgy and Inorganic Polymers:

Occurrence, isolation, purification,

properties and uses of the following metals and their important compounds: Zr, Ge, Pu, Th, U and Os. Silicates: Various silicate structure- property correlation- silicones polyacidsstructure of heteropoly and isopolyacids- Polymeric sulphur nitride-borazines phosphonitrilic compounds- boranes and carboranes

REFERENCE BOOKS: 1. Jame E. Huheey, Inorganic Chemistry: Principles of Structure and Reactivity (Harper Collins) 2. K.F. Parcel and J.C Kotz, Advanced Inorganic Chemistry (Saunders Golden) 3. G.C.Demitrass et.all, Inorganic Chemistry,(prentice Hall). 4. B.E Douglas, D.H.Mc. Daniel and J.J Alexander, Concepts and Models of Inorganic Chemistry. 5. H.J Emeleus and A.G. Sharpe, Modern Aspect of Inorganic Chemistry. 6. M.C Day Jr and J. selbin, Theoretical Inorganic Chemistry, East West Press. 7. F.A. Cotton and Wilkinson, Advanced Inorganic chemistry, John Wiley. 8. N.N.Greenwood and a Earn show, chemistry of Elements, pregamon. 9. L.Araroff, Introduction to solids, Tata Mc Graw Hill. 10. 11. 12. 13. C.Kittel, Introduction to Solids State physics, Wiley Eastern. A.F Wells, Structural Inorganic Chemistry, ElBS. M.V. Keeer, Principales of the Solid state, Wiley Eastern. A.R. West Solid State Chemistry and Application ,Plinom.

14. 15. 16. 17. 18.

D.k. Chakrabarthy, Solid Stete chemistry Ne Age International. S.Glasstone, Sources Book on Atomic Energy .East West Press. H.L Armiger, Essential Of Nuclear chemistry, Wiley Eastern. G.Fridlander, J.W Kennedy E.S.Macias and J.M.Miller. Nuclear and Radio chemistry. John Wiley and Sons.

SUBJECT CODE: 1.3 SUBJECT: PHYSICAL CHEMISTRY-I UNIT I Thermodynamics: Thermodynamics of the system of Variable Composition.

Partial Molar quantities a partial Mol or volume , Experimental determination, chemical potential, Gibbs Duhem Equation- Thermodynamic properties of real gases- Fugacity, Determination of fugacity of real gases, the concept of activity for condensed states, Thermodynamic equation of states- derivation and application. Maxwell there modynamic relations. Thermodynamic Properties at absolute Zero: De Dondee treatment of

Chemical Equilibrium-non equilibrium thermodynamics, entropy production, on sager Reciprocal Relationship. Three compound system-Partially miscible three liquid systems, formation of one pair two Paris and three pairs of partially miscible liquids. System composed of two solids and a liquid. Gystallisation of pure components only, formation of solid solution and partial miscibility of solid phases. UNIT II Quantum Mechanics-I: Postulates of quantum mechanics. Schrdinger time independent equation Wave function Operation- Linear and hermit an Operator, Method of settings up quantum mechanical operation. Eigen Function and Eigen values. Degeneracy, Orthogonality and normalisation of wave function .commuting and non-commuting operators. Non-commuting operators and uncertainty principle. Application of Quantum mechanics of simple system free particle, particle in ID Box, particle in 3D (Cubic box and rectangular) Box, simple harmonic oscillator rigid rotator and hydrogen atom.

UNIT III Quantum Mechanics-II: Approximation method- Perturbation theory (first

order only) and variation method secular equation and secular determinants. Helium atom and Effective nuclear charge. Electron spin and Paul is principle Slater determinant, Born- Oppenheimer approximation. Hatree Fock self Consistent Field methods of many electron systems. LCAO approximation MO methods for H2+H2
VB

treatment of hydrogen molecule .Hybridisatiin. Huckel

theory of conjucated systems bound order and charge density calculation, Application to ethylene and butadiene. UNIT IV Statistical Thermodynamics: Aim of Statistical thermodynamics. Boltzman

distribution law and its derivation. Partition function. Derivation of expression for translation; rotational and vibrational partition function. Thermodynamic properties from partition function. Quantum statists Fermi Dirneand Bose Einstenin and Debye theories of heat capacities of Solids UNIT V Electrochemistry: Debye Huckel theory of ion interaction derivation and

experimental verification activity co-efficient Debye Huckel Limiting Law. Modification of Debye Huckel Limiting law. Kinetics of electrode processesButler- volmer equation Tafel curves electrical double layer Zeta PotentialElectro kinetic Phenomena Vollammetry and Paleography current voltage relationships, dropping mercury electrode, half-wave potential , Application of Polargraphy,

Coulometry- Primary and secondary coulometric analysis, anperometric titrations, chronopotentiometry - cyclic voltammery Electrochemical energy conversion- storage and fuel cells Thermodynamics of fuel cells REFERENCE BOOKS:

1. S.Gasstone Thermodynamic for chemists. 2. S.Glasstone-An introduction to electro chemistry. 3. B. Viswanathan, etal Electro chemistry. 4. DR Crow, Principles and Application of Electrochemistry 5. L.Antropov,Theoretical electrochemistry. 6. A.k Chandra, Introductory Quantum chemistry. 7. J, Raja ram and J. Kuriacose, chemical Thermodynamic. 8. I.N. Levine, Quantum chemistry.

SUBJECT CODE: 1.4 SUBJECT: ENVIRONMENTAL CHEMISTRY UNIT I Environmental and Ecosystem: Introduction to Environmental chemistry Its Concept and scope; environmental segments- atmosphere, hydrosphere, lithosphere and biosphere. Environment and ecosystem; biogeochemical cycles of water and elements C, N, O, S and P. UNIT II Atmosphere and air Pollution: Evolution chemical composition and structure of atmosphere chemical and photochemical reactions in atmosphere oxides of S,N and C and their effect; green house gases and global warming ;photochemical smog, acid rain and ozone hole formations. EI Nino

Phenomennon; partilates and activity in atmosphere. Analysis and Control of Air Pollutants .Air Pollution episodes-TCDD,Bhopal and Chernobyl disasters. UNIT III Hydrosphere and water polluction: Various water resources and their

characteristics; water polluction-source and classification; organic, inorganic and radioactive pollutants; samping and analysis of water pollutants; water quality parameters and standards; determination of water quality parameters. Fluorosis and defluoridation; water treatment processes and preservation. Some case studies of water pollution. UNIT IV Lithosphere and soil pollution: Chemical composition; micro and macro

nutrients in soil pollution by fertilizers, persticides, plastics and heavy metal compounds. Plants as indication of soil polluction. Natural resources Mineral resources metals and non-metals; fuel and energy resources coal,

petroleum, natural gas, solar energy, hydrogen from water cleavage and tidal and wind energy. Natural organic and inorganic vermicompost fertilizers. Biofertilisers blue-green algae rhizobium, azospirillum and phospobacteria. UNIT V Environmental Restoration: Environmental resotation waste disposal and their management by chemical and biological methods, recycling and further use of waste; conservation of forests and wild life. The state of global environment and earth summit. Indias effort in environmental protection the environment act 1986 and its amendment; participation of voluntary agencies in environmental protection.

REFERENCE BOOKS: 1. A.K.De, Environmental Chemistry, New Age publishers, New Delhi, 3rd edn.3rd reprint 1996. 2. B.K.Sharma and H.Kaur, Environmental Chemistry, Goel publishing House, Meercut, 3rd edn.1996-97. 3. G.S.Sodhi, Environmental Chemistry, Narosa publishing House, New Delhi, 2000. 4. C.Baird, Environmental Chemistry, W.H.Freeman and Company, New York 1995. 5. E.P.Odum, Fundamentals of Ecology, W, B.Saunders publications. 6. S.S.Dara, A textbook Of Environmental Chemisrty And Polluction Control, S.Chand & Company, New Delhi.

SUBJECT CODE: 1.5 SUBJECT: PRACTICALS I ORGANIC CHEMISTRY

a) Separation and Characterisation of two Component mixtures b) Two Stage preparations involving nitration, brominating, diazotization, rearrangement and aceylation. c) Separation of binary mixture (separation to be given in semi-micro quantity only report and complete separation of the components required -15% marks d) A bifuncational Organic substance will be give separately for analysis. Derivational to be reported -25% marks e) Preparation involving 2 stages- Recrystallisation final Product and the Crude Products are to be exhibited f) Viva Voice g) Record -20% marks - 20% marks. -20% marks

IYEAR-II Semester SUBJECT CODE: 2.1 SUBJECT: ORGANIC CHEMISTRY II UNIT I UV, IR & Mass Spectroscopy: Absorption spectra of conjugated dienes & , unsaturated carbonyl compounds Woodward fieser rules spectra of aromatic and heterocyclic compounds Scotts rule solvent effects. Vibrational frequencie of alkenes, aromatic compounds, alcohols, ethers, phenols, amines, acids, esters & amides. Effect of hydrogen bonding & solvent effects on absorption frequencies Fermi resonce. Molecular ion peak base peak metastable peak nitrogen rule Mc, Laffertly rearrangement isotopic peak fragmentation pattern of organic compounds.

UNIT II
1H-NMR, 13CNMR,

ORD & C,D:

1HNMR

Principles of NMR Chemical shift

spin spin coupling, delta & tall values of aliphatic, olefinic, aromatic, carboxylic, enolic, phenolic, alcoholic protons. Chemicals exchange deuteration simplification of complex spectra double resonance- shift regents.
13C

NMR chemical shift & coupling constants of

aliphatic, aromatic & carbonyl carbons. ORD & CD principle Types of ORD curves , haloketone rule octant rule applications of these in the determination of configuration & conformation of simple monocyclic & bicyclic ketones.

UNIT III Terpenes: Structure and synthesis of , pinene, zingiberene, r-bisabolene , santornine, abietic acid Biosynthesis of alkaloids.

Steroids: Classification structure elucidation of cholesterol synthesis of orgosterol and roster one, testosterone, estrone & progesterone bilacids. Prostaglandin: General study structure & synthesis Of PGEI & PGFI Vitamins: Vitamins AI, BI, B2, B6, C, D, &B

UNIT IV Organic photochemistry: Thermal & photochemical reactions Allowed & forbidden transition - Jablonski diaglran, photochemical reactions of mentones photosensitization - Norrish Type I & II reactions paterno Buchi reaction Per cyclic reaction conservation of orbital symmetry electro cyclic reactions cycloaddition reactions and sigma tropic rearrangements Applications of correlation diagram approach, Huekel Mobius approach to the above reactions. Molecular Rearrangement: Migratory aptitude of groups Mechanisms of the following rearrangements Wagner meerwin, Demjanov, Baeyer villager oxidation Favorski, dienone phenol, di - Ullmann, Hunsdiecker, Hofmann Lofler Freytag reactions.

UNIT V

Reagents in Organic synthesis:

Use of the following reagents in organic

synthesis complex metal hydrides lithium dimethyl cup rate, lithium diisopropylamide, DCC, Trimethyl sily lodide, DDQ, SeO2,peterions synthesis Organiometallic reagents menthy1 lithium, aluminum tertiary but oxide, aluminum isopropoxide. Planning synthesis: Synthon synthetic equivalent Relay, Linear &

Convergent synthesis functional group Interco version use of activating & blocking groups streoselective problems of geometrical & optical isomerism retrosynthetic anaylsis of Bisabolene & cis jasmine. Transition metal complexes in organic chemistry homogeneous hydrogenation diastereo selectivity enantioselectivity.

REFERENCE BOOKS: UNIT I & II 1. Application of Absorption Spectroscopy. 2. J.R.Dyer, prentice Hall. 3. Organic Spectroscopy W.Kemp Palgrave Third Edition 4. Spectrometric Identification of Organic Compounds S.M, Silverstein, G.V.Bassler and T.C.Morril Willy. 5. Interpretation of Carbon 13 Spectra 6. F.W.Whirli and T.Wirtilin 7. Organic Spectroscopy V.R.Dani tata Mc Graw Hill publishing company Ltd. 8. Spectroscope methods in organic chemistry D.H. Williams and lan Fleming, tata Mc.Graw Hill.

9. Elementary Organic spectroscope principles and chemical applications. Y.R.Sharma S.Chand & Co. 10. Organic spectroscopy principles and application. - Jag mohan

narosha publishing house. 11. Hill. 12. Mass spectrometry principles and applications I, Howe, D.H. Stereo chemistry of carbon compounds E.L.Eliel Mc Graw

Williams and R.D.Bowen Mc graw Hill. 13. 14. Organic chemistry Vol II I.L.Finar,ELBS ORD and CD in chemistry and Biochemistry Academic press.

UNIT III 1. Organic Chemistry Vol II I.L, Finar ELBS. 2. Chemistry of Terpenoids Paul de mayo Vol I & II Academic press. 3. The Chemistry of Organic Natural Products O.P.Agarwal Goel publishing house. 4. Steroids L.Fieses and mary fiese Reinhold 5. Steroids Shoppe 6. The Chemistry Steroids W.Klyne Methuen and Co, New York. 7. The Prostaglandins Vol I 8. Ram well Plenum press. 9. Principles of Organic synthesis R.O.C.Norman 10. 11. UNIT IV 1. Organic Photochemistry J.M.Coxton, B.Halton Cambridge University press. 2. Organic Chemistry R.T.Morrison and R.N.boyd prentice, Hall. 3. Organic Chemistry H.Pine Mc Graw Hill 4. Molecular Reaction & Photochemistry C.H.Depuy & O.L.Chapman prentice Hall. 5. Reaction Mechanism in Organic Chemistry. S.M.Mukherji & S.P.singh 6. Pericycle reactions. Mukherji & singh. 7. The Conservation of Orbital symmetry R.B. Woodward & Hofmann. 8. Verlog Chemic Gmbh & Academic Press. The Chemistry of vitamins S.F.Dyke Intersience. Medicinal Chemistry A. Burger academy press.

9. The Importance of Antibonding orbitals - H.H.Jaffe & M.Orchin. 10. An Introduction to conservation of Orbital symmetry. A.J.Bellemy

Longman 11. 12. 13. 14. Aspect of Organic Photochemistry - William M. Horse pool. Academic press London. Advanced Organic Chemistry J. March Wiley. A Guide book to mechanism in Organic Chemistry peter sykers

Orient Longman 15. Holt &co 16. 17. 18. 19. 20. Reaction Mechanism & structure in Organic Chemistry Gurdeep R.Chatwal.Himalaya publishing house. Organic Chemistry Vol I.L.Finer ELBS Molecular Rearrangments P.De Mayo Organic Reaction and Reagents J.N .Gurtu, R. Kapoor - S.Chand Mechanism & structure in Organic Chemistry E.S.Goud Henry

& Co. (p) Ltd. 21. Name Reaction & Mechanism (Vol I & II) - J.N.Gurtu, S.C. Rastogi

S.K.Agarwall - Pragati prakashan. UNIT V 1. Advanced Organic Chemistry J.March - Wiley 2. Reaction Mechanism and reagents in Organic chemistry guedeep Rchatwel. Himalaya publishing house. 3. Organometallics in Organic synthesis. J.M.Swan & D.St.C.Black

Chaman & Hill text Book series.

4. Organometallic chemistry gurdeep Chetwall, Y. Yadav. Himalaya publishing house. 5. Priciples of Organic Synthesis R.O.C.Norman Chapman & Hill, London, 6. Some Modern Methods of organic Synthesis W.Curruthers-Cambridge, University press. 7. Advanced Organic Chemistry part B, F.A.Carrey & R.J.Sundberg. 8. A programmed synthon Approach S. warren John Wiley & sons. 9. Organic synthesis R.E. Ireland. Prentice Hall of India (P) Ltd. 10. 11. Organic chemistry, R.T.Morrison & R.N.Royd Prentice Hall Guide Book to Organic Synthesis R.K.Malki & D.M.Smith ElBS

Longman. 12. Organic synthesis Michael B.Smith, Mc.Graw Hill, International

Edition.

SUBJECT CODE: 2.2 SUBJECT: INORGANIC CHEMISTRY II UNIT I Coordination Chemistry Stability and Reactions: Stability and instability of complexes- determination of stability constants by potentiometric and spectrophotometric methods, factors stability chelate and template effects. HSAB concept and Symbiosis: theretical basic of softness and hardness; stabilization of Unusual Oxidation states. Kinetic stability Lability and interness, Ligand Substitution reaction of square planar complex Factors affecting reactivity of square planar complex Substiution reaction in octahedral complexes- acid hydrolysis ,base hydrolysis and anation reactions . Electron transfer reaction Complementary and non- complementary reactions. Inner sphere and out sphere processes; outer sphere process in photochemical reactions.

UNIT II Spectral Methods I: Electronics spectroscopy L.S. coupling and j-j coupling schemes, microstates, Hunds rules and Term symbols; selection rules for electronic transition and hole formalism; or gel and Tanabe Sugano diagrams; evaluation of 10q and B for Octahedral d2 and d8 systems. Change transfer spectra; electronics spectra of lanthanide and actinide complexes. Optical isomerism in octahedral chelate complex, their absolute configuration determination from ORD and CD methods; information of chelate complexes.

UNIT III Spectral Methods II: Mossbauer spectroscopy; principles isomer shift,

quadrupole and magnetic interactions MB spectroscopy of octahedral high and low spins Fe (II) and Fe (III) complexes. Information on oxidation state, piback coordination and structure in iron compounds. Studies on halides of tin (II) and tin (IV). NMR : Application of chemical shift and spin spin coupling to structure determination using multi probe NMR (1H,31P,19F,15N) ; effect of quardrupolar nuclei on NMR spectra. NMR studies on Chemical exchange and dynamic processes in organic and organ metallic compounds; NMR studies on fluxional molecules .Paramagnetic NMR and contact shifts; lanthanide shift reagents. EPR.Application of hyperfine splitting and g-factor to structure determination zero - Field splitting and Kramers degeneracy. Covalency of M-L Bounding by EPR study. Application of EPR in the study of J.T distortion in Cu (II) complexes.

UNIT IV Instrumental Analytical Techniques: (Instrumental aspects not required): Spectroanalytical techniques: Principle and application of colourimetry,

spectrophotometer and fluorimetry. Flame photometry techniques: atomc absorption, atomic emission and atomic fluorescence spectroscopy. Light scattering techiniques: nephelometry and turbidimetry.

Theromonaltical techniques: TGA, DTA and DSC methods. Electro analytical techniques .Electrochemical cell and electrode potentials; electrochemical series and application of redox potential to inorganic reaction systems.

Classification into constant current and controlled potential techniques. Voltammetry, cyclic voltammetry and stripping Voltammetry; amperometry and chronopotentiometry potentiomery and ionselective electrodes (halide and alkali ions).

Principle and operation of column, thin-layer and gas chromato graphic methods HPLC and HPTLC; application to inorganic substances principle and application of ion exchange and solvent extraction methods. UNIT V Organ metallic Chemistry: Introduction, EAN rule and its correlation to

stability. Metal carbonyls-synthesis, properties structure and bounding and isolobal analogy, IR study of metal carbonyls .m-Pi acid complexes Preparation, properties and structure features of complexes with alkenes, alkyne, allyl and areane system.Metallocenes - systhesis , properties and bounding beryllocene. Substitution reaction of carbonyls: oxidative add ional and reductive structure inferrocence; covalent versus ionic bounding in

ellmination, insertion and elimination reaction nucleophillic and electrophillic attack of coordinated ligands Homogeneous catalysis: alkene hydrogantion and synthesis Gas: hydroformylation carboxylation of alcohols and oxygenation of olefins. Hetrogenous catalysis: Fischer Tropsch process Ziegler- Natta

Polymerisation.

REFERENCE BOOKS: 1. D.f Shriver, P.W.Atkins and C.H.Longfor, Inorganic chemistry, Oxford 1990. 2. W.L.Jolly,Moder Inorganic Chemistry ,MC Graw Hill company , 2nd Edn, 1991 3. J.E. Huheej, E.A.Keiter and RL Keiter, Inorganic chemistry, Harper and row/Pearson Asia, 2, 3, & 4th Edn 1993 4. F.A. Cotton and G.Wilkinson, Advanced Inorganic Chemistry, john Wiley and sons, 3, 4, & 5th edn 1988. 5. B.E Douglas ,D.H.Mc Daniel and J.J Alexander Concepts and Modals of Inorganic Chemistry .John Wiley & Sons ,2 Edn.1993 and 3 1994. 6. R.S Dago,Physical Methods in chemistry ,W.B Saunders 1977 7. E.A.V Ebsworth et al,structure methods in inorganic chemistry ,ELBS 1987 8. H.H.Willard ,L.L Merritt J.A Dean and F.A Settle Instrumental methods of Analysis 6th edn CBS publishers 1986 9. Vogels text book of Quantitaative chemistry analysis. Revised by G.H.Jeffery. J.Bassett J.mendhan and R.C Denney ElBS 5th ed 1989 10. D.Askooog and D.M.west, Principles of Instrumental Analysis

,Holt-Saunders,2 edn 1980 11. D.A skoog and J.J Leary, Instrumental analysis, Saunders college

publishing 1992.

SUBJECT CODE: 2.3 SUBJECT: PHYSICAL CHEMISTRY II UNIT I Chemical Kinetics: Simple collision theory, absolute reaction rate theory

(ARRT), thermodynamic treatment, potential energy surfaces, application of ARRT to simple biobimolecular processes; chain reactions general

characteristics, study of kinetics of chain reaction like H2-Br2 reactions, decomposition of acetaldehyde and H2O4 ; study of H2-O2 explosive reactions. Theory of unimolecular reactions Lindemann, Hinshelwood, RRKM and stator treatments; steady sate approximations, principles of microscopic reversibility and detailed balancing, kinetic isotope effect; Reactions in solution, factors influencing reaction rate in soluction, ARRT to reaction in solution, significance of volume of activation, primary and secondary salt effects. Homogeneous catalysis, acid-base catalysis, acidity function, Bronsted

catalysis law. Fast reaction techniques chemical relaxation methods, temperature and pressure jump methods, ultrasonic absorption technique, reactions in flow system, continuous and stopped flow shock wave tube methods, chemical kinetics in crossed molecular beam.

UNIT II Photochemistry and Radiation Chemistry: Physical properties of the

electronically excited molecules Excited state dipole moments, excited state pka, excited state redox potentials. Photophysical processes in electronically excited molecules fluorescence, phosphorescence and other deactivating processes, stern volmer equation and its applications, electronic energy transfer mechanisms.

Photosensitisation

and

chemiluminescenc.

Experimental

techniques

in

photochemistry-light sources, chemical actinometry, conventional photolysis procesure flash photolysis techniques. Study of photochemical reactions lik H2X2 decomposition of photosynthesis, photochemical conversion and storage of solar energy. Radiation chemistry source of high energy, interaction of high energy radiation with matter, radiolysis of water, definition of G-value, mode of reactions of hydrated electrons. OH and H-Experimental techniques on radiation chemistry, dosimetry, Elementary aspects of radiation chemistry in biology and industry.

UNIT III Group Theory: Group theory: Molecular symmetry elements and symmetry

operation, vector and matrix algebra, symmetry operations and transformation matrices; group theory- definition and properties of a groups symmetry. Point groups, representation of a group-reducible and irreducible representations, great orthogonality theorem, characters, construction of character. Tables, direct product groups. Symmetry of normal modes of vibrations, applications of group theory to normal mode analysis, symmetry properties of integrals, applications for spectral selection rules of vibration spectra-IR and Ramam active

fundamentals, symmetry of molecular orbital and symmetry selection rule for electronic transition in simple molecules (ethyleneFoemaldehyde, benzene and nphthaiene), Group theory and quantum mechanics wave functions as a basis of irreducible respresentations, group theory as applied to hybrodisation, HMO theory and HMO calculation and delocalization energy for ethylene,

eyclopropenyl and butadiene systems. UNIT IV

Spectroscopy I:

Elements of molecular spectroscopy: Absorption and

amission of radition, the time depaenent Schrodinger equation, interaction of EMR with matter, Einstein coefficient, induccdemission and absorption, ultra were, IR and Raman spectroscopy if diatomic molecules-determation of normal molecular parameters, virational spectra of polyatomic molecules-definition of normal modes and normal coordiates, IR and Raman active fundaments, overtone and combination bands-concept of group frequencies, couping interaction bands Fermi resonance, basic concept of FT-IR. Electronic spectra of diatomic and polytomic molecules, born-oppenheimer approximation, Franck-Condon principle, dissoci energy, Rotational fine structure and fortrat diagram.

UNIT V Spectroscopy II: H1-NMR, Introduction, Theory of splitting of Nuclear zeeman levels in a magnetic field, chemical shift, spin-spin splitting, dipolar interaction, reaction times, line shape and line width, experimental techniquesdouble response technique, ENDOE, overhauser, effect, FT-nmr spectroscopyLanthanide shift reagen ESR spectroscopy-hyperfine spiltting, factors affecting the maginitude of the g values, solid state epr, rate of electon exchange reaction, fine structure and hyperfine structure. Electron density from esrspectra of free radic also Photoelectron spectroscopy-basic principles, instrumentation X-ray

photoelectron and unphotoelectron spectra, core energy level studies application of ESCA; laser, Raman spectroscopy theory of Raman scattering, techniques and instrumentation, the laser source, applications if laser Raman spectroscopy, structure determination. REFERENCE BOOKS:

1. K.J. Laidler, chemical kinetics, 2nd edn., Tta Mc Graw Hill, New Delhi, 15th reprint 1991. 2. K.J. Laidler, Theories of chemical Reaction rates; Mc Graw Hill; New York, 1969 3. K.K. Rohatgi Mukerjee, fundamentals of photochemistry. 4. J.N. Bradley, fast Reaction 5. N.J. turo, Modern Molecular photochemistry 6. F.A.Cotton, chemical Application of group Theory. 7. C.N. Banewell, Spectroscopy, Vol. 1, 2, &3. 8. Stanghan and Walker, Spectroscopy, Vol. 1, 2, & 3.

SUBJECT CODE: 2.4 SUBJECT: BIO ORGANISM BIO INORGANIC, AND BIO PHYSICAL CHEMISTRY BIO ORGANIC CHEMISTRY UNIT I Nucleic Acids: Purine and pyrimidine bases of nucleic acids.

Nucleosides, base pairing via H bonding. Primary and secondary structures of DNA and RNA. Forces responsible enzymatic method, PCR technique in chain amplification. UNIT II Carbohydrates and Lipids: A. Carbohydrates: Structure and Storage polysaccharides starch, chithin and glycogen. biological functions of glucosaminoglycans or

mucopolysaccharide. Carbohydrates of glyeoproteins and glycolipids. Role of sugars in biological recognition. Blood group substances. Carbohydrate metabolism: Krebs cycle, glycolysis, glycogenesis and

glycogenolysis, gluconeogenesis; pentose photospate pathway. B.Lipidas: Fatty acids, essential fatty acid, structure and function of triacylglycerols, glycerophospholipids, sphingolipids, cholesterol, bile, acids, prostaglandins, lipoproteins composition and function, role in

atherosclerosis. Biological membranes. Fluid mosaic model of memberane structure. UNIT III Bioinorganic Chemistry I: Non metals and metals in biological system;

essential and trace elements. Classification of metalloid molecules non

proteins, proteins and enzymes. Metallobiosite, its coordination environment and enatatic state. Dioxygen binding and transport heme proteins: myoglobin and hemoglobin, their structure, function and physiology; non-heme proteins: hemerythrine and hemocyarmin.

Biochemical iron storage and transport by Transferring and siderophores; metal ion exchange activity of siderophores. UNIT IV Bioinorganic Chemistry II: Electron transfer in biological systems prophyrins and cytochromes; Fe s cluster proteins (Ferredoxins and rubredoxins) and their synthetic model; blue copper proteins. Photosynthetic pathway chlorophyll, PSI, PSII and involvement of Mn complex and Cytochrome Coxidase. Vitamin B12 and coenzymes; in vitro and vivo nitrogen fixation UNIT V Biophysical Chemistry: Thermodynamics in biology energy flux transfer of potentials and coupled reactions role of singlet oxygen in biology general principals of function and structural organization in bioenergetic fundamental reactions structure of membranes (introductory aspects only ) solute transport across membranes membrane potentialsion pumps biophysical applications of moussbauer effect. REFERENCE BOOKS: UNIT I & II:

1. G.L.Zubay, W.W. parson and D.E.vance, Principles, of Biochemistry, Wm.C.Brown Publishers 1995. 2. G.L.Zubay, Biochemistry, WM.C.Brown publishers, Chicago, 1998 3. L.Stryer, Biochemistry (4th . end) W.H.Freeman and company, 1995 UNIT III & IV: 1. D.E.Fenton, Biocoordinaion Chemistry, Oxford Chemistry, Primar Series, Oxford Science publications, Oxford 1995. 2. W.LJolly, Modern Inorganic Chemistry ,MC Graw Hill Company 2Nd edn 1991 J.E Huheey, E.A Keiter and R.L Keiter, Inorganic C

SUBJECT CODE: 2.5 SUBJECT: PRACTICAL II- INORGANIC CHEMISTRY Skill development is in the following laboratory, experiments are required 1. Qualitative (systematic) analysis of inorganic mixture containing two less familian cation. The cation can be W,Tl.Te,Se,Mo,Ce,Th,Zr,V ,U,Ti &L 2. Direct cation can be (Back titration methods of estimation of ca, Zn Cu By EDTA titration. 3. Separation and estimation of minutures by volumetric and gravimetric Methods a) Cu 2 + & Ni 2+ b) Fe 2 +& Cu 2+ c) Cu2 +&Zn 2+ 4. Preparation complexes) The university Examination will consist of a) Qualitative analysis will consist of familiar captions: 25% Marks b) EDTA titration or separation and estimation of one :25% Marks Mention in a mixture of two Preparation of complex: 10% Marks Viva Voice Record : 20% Marks : 20% Marks of Inorganic metal complexes (at least 10 different

IIYEAR-III Semester SUBJECT CODE: 3.1 SUBJECT: ORGANIC CHEMISTRY III Unit I Introduction to Spectroscopy Techniques Electronic transmission in enes. eones and arenes, Woodward Fieser rules effect of solvent polarity on UV absorption- principles of characteristic group frequency in IRidentification of functional groups and other structural features by IR- Hydrogen bonding and IR bandssampling techniquesFTIR and its Instrumentation-Organic Mass Spectroscopy- EI, CA, FAB, electro spray and MALDI ion sources- Magnetic High resolution (Double focusing), TOF and Quadrupole Mass Analysers- Charecteristic fragmentation modes and MS rearrangement MS-GC, HPLC-MS, TG-MS Unit II NMR spectroscopy and structure elucidation, Chemical shifts- anisotropic effect and coupling constants in organic compounds, spin-spin interaction in typical systems- analysis of 1st order spectrasimplification methods for complex spectra- use of high field NMR- shift reagents, chemical exchange and double resonance- introduction to FT (pulse) NMR, NOE, DEPT and 2DNMR, 13C NMR and 13C Chemical shifts - spectral interpretation and structure identification- spectral interpretation using actual spectra taken from standard texts- solving of structural problems on the basis of numerical and spectrum based data- NMR Spectroscopy of N, F and P Unit III

Reagents and Organic Synthesis: Application of Hydrogenation catalystsHindered Boranes- Bulky metal hydrides- NaCN, BH3, DIBAL, Li trialkyle borohydrides, tri-n-butyl tin hydride, diimide, Lindlar catalysts and Rosenmund redudctions,McFedeyan-stevens reactionOxidation using SeO2, lead tetraacetate, Ozone, peracids, DDQ and Cr(IV) reagents- Swern Oxidation, Moffattt oxidation, allylic and benzylic oxidation- sommelet reaction- elbs reaction- oxidative coupling of phenols- sharpless asymmetric epoxidation- chemo and regioselectivity in reduction and oxidation, use of XeF2, SbF5, VF5, MoF6, CF3OF, SF4, HF as fluorinating agents.

Unit IV Chemistry of Polymers: Type and mechanism of polymerization reaction- Step growth, free radical, addition, ionic, ring opening and group transfer polymerizations- Copolymers- characterization of polymers- methods of measurement of molecular mass and size- stereochemistry of polymers- stereo regularity and its control- Zeigler Natta Catalyst- Gelation and network formation- polymer architecture- configuration and conformation, frictional properties and mechanical properties- glassy and rubbery states- visco electricity- crystallization and melting of polymers- relation between structures, property and performance- manufacture and application of polyolefins, thermoplastics, polyamides, polyesters, polyurethanes, epoxides and industrial polymers.

Unit V Heterocyclic Chemistry Nomenclature of Heterocycles, Replacement and Systematic Nomenclature, Hantzsch Widman system for monocyclic, fused and bridged heterocycles. Structure, Reactivity, Synthesis and reactions of the following four membered heterocycles Oxitanes, Azetidines and Thietanes ; Five membered heterocycles Imidazoles, Pyrazolines, 1,2,4- Triazoles, 1,2,3-Triazoles, Oxadiazole and Thiadiazole; Selenophenes, Tellurophanes and their benzo derivatives; Six membered heterocycles Pyrones, 1,2,3, 1,2,4- and 1,2,5 Triazines , Pyrimidines and Pyrazines; Seven membered heterocycles Azepines, Oxepines and Thiepines. Fused heterocycles : Indole, Benzofuran , Quinoline, Isoquinolines and Coumarins. Naphthyridines Synthesis and reactivities.

Books for study Pavia Lapman Kriz Vyvyan-Spectroscopy-Ceengage Learning W Kemp-Organic Spectroscopy-Palgrave. J March-Advanced Organic Chemistry-Wiley. R O C Norman and A Coxon-Modern Synthetic Reactions-Chapman and Hall. M B Smith-Organic Synthesis-McGraw Hill. R K Bansal-Synthetic Applications in Organic Chemistry-Narosa.

Robert M. Silverstein,Francis X. Webster and David Kiemle. "Spectrometric Identification of Organic Compounds Wiley 2005 R K Mackie, D M Smith and R A Aitkan-Guide Book to Organic SynthesisLongman, 2nd Edn. R J Simmonds, Chemistry of Biomolecules-Royal Society of Chemistry. R J Young-Introduction to Polymer Science-John Wiley and Sons. F W Billmayer-Text Book of Polymer Science- John Wiley and Sons. G Odian-Principles of Polymerization- John Wiley and Sons. J M G Cowie-Polymers: Chemistry and Physics of Modern Materials-Viva. K J Saunders-Organic Polymer Chemistry-Chapman and Hall. Dr. Jagadamba Singh and Dr. L.D.S Yadav-Organic Synthesis-Pragathi Prakashan. Maya Shankar Singh-Advanced Organic Chemistry-Pearson. Donald L. Pavia, Gary M. Lampman, George S. Kriz and James R VyvyanSpectroscopy-Cengage Learning.Ratan Kumar Kar-Applications of Redox and Reagents in Organic Synthesis-New Central Book Agency. J. Joule and G. Smith-Heterocyclic Chemistry-Van-Nostrand, ELBS. Acheson-An Introduction to Heterocyclic Compounds-Wiley-Eastern. Ahluwalia and Parashar-Heterocyclicc and carbocyclic chemistry- Ane Books.

Jagadanba Singh and Yadav-Organic Synthesis-Pragati Prakashan Meerut S.K Ghosh Advanced General Organic ChemistryPart1and11 New Central BookAgency

IIYEAR-III Semester SUBJECT CODE: 3.2 SUBJECT: INORGANIC CHEMISTRY III

UNIT I

Metal Extraction by reduction of oxide ores Thermodynamic aspects of extraction. Ellingham diagrams Chemical and electrolytic reductionreduction potentials effect of complexation- Latimer and Frost diagrams trends in stability of oxidation states, stereo chemistry and ionic sizes of transition metals. Comparison of 3d, 4d and 5d series by taking Ti subgroup as examples. Lanthanides: Electronic structure, oxidation states Chemical Properties of +2, +3 and+4 oxidation states Lanthanide and actinide contraction- spectral and magnetic properties. Coordination number and stereochemistry of complexes. Actnides: Electronic structure- Oxidation states Lanthanide and actinide contraction spectral and magnetic properties in comparison with those of lanthanide and d-block elements. Trans- actinide elements IUPAC nomenclature Periodicity of trans actinide elements. Beach sands of Kerala Important components and their separation Utilization of monazite illmenite,zircon and sillimanite.

UNIT II

Inorganic polymers: Types of Inorganic polymers Characteristics of polymers - molecular masses and their distribution structural features chain characteristics - solubility consideration crystalline and mechanical properties. Polyphosphazenes - Synthetic routes to various types of Polyphosphazenes important applications of these Polymers water soluble bioactive Polymers Organometallic Polyphosphazenes Polymer bound platinum anti tumour agents. Polysiloxanes and related Polymers preparation, structural features and uses Polysilanes and related Polymers Chemical modification of Polysilanes Electrical conductivity and photo conductivity Polysilanes as photo resists and photo inhibitors.

UNIT III Organometallic chemistry: Compounds with metal to Carbon single bonds alkyl and aryls of main group elements Transition metal to carbon multiple bonds - Metal carbonyls, cyanides and isocyanides Usefulness of eighteen electrons rule to predict formulae and stability of organometallic compounds. Transition metal complexes with alkenes, alkynes, alkynes, allyl, diene, dienyl and trienyl radical Cyclic complexes with cyclobutadiene, cyclopentadienyl,arenes, cycloheptatrienyl cycloctatetraene

and cyclooctatetraenyl dianion. Preparation, properties, nature of bonding and structural features Fluxionality in complexes catalysis by organometallic compoundshydrogenation, hydroformylation and polymerization reactions.

UNIT IV

Bioinorganic Chemistry I Role of metal ions in the biological system. Essential and nonessential elements macro minerals and essential trace elements synergism and antagonism among essential trace elements. Metal deficiency and diseases related iron, Zinc and copper deficiency metal ion toxicity copper over load and Wilsons disease iron toxicity toxicity of arsenic, cadmium, mercury and lead. Metal complexes in medicine Chelation therapy BAL, penicillamine, Polyamino carboxyclic acids and desferrioxamine gold compounds and rheumatoid arthritis platinum complexes as anticancer, drugs metal complexes in radio diagnosis and magnetic resonance imaging. Metal storage and transport: Iron storage and transport transferrin, ferritin and sideropheres. Other storage and transport systems ceruloplasmin and serum albumin for copper, metallothioneins and phytochepatins vanadium storage and transport. Transport and storage of dioxygen hemoglobin and myoglobin structure and functions structural

model for dioxygen binding co-operativity, Perutz mechanism and Bohr effect synthetic oxygen carriers. Other natural oxygen binding proteins hemocyanin and hemerythrin synthetic model for hemocyanin.

UNIT V 14 HOURS Bioinorganic Chemistry II Electron transfer in biology structure and functions of electron transfer proteins Cytochromes and respiratory chain, iron-sulphur proteins rubredoxin and ferridoxins synthetic models (for Fe4S4 cluster only) blue copper proteins. Nitrogen fixation: Invitronitrogen fixation through dinitrogen complexes nitrogen fixing micro organisms nitrogenases model compounds. Photosynthesis: Structure of Chlorophyll Photo systems I & II Light reaction role of manganese enzymes in the cleavage of water. The Z scheme dark reactions. Metalloenzymes: Structure and functions of the following enzyme carbonic anhydrase, carboxy peptidase, alchoholdehydrogenase, catalalse and peroxidase, Cytochrome P450, super oxide dismutase and xanthin oxidase B12 coenzymes B12a, B12x, B12r and methyl cabal amine biomethylation.

REFERENCES

1.J.E. Huheey, E.A Keiter and RL Keiter: Inorganic chemistry Principles of structure and Reactivity Pearson Education

2.DF Shriver, PW Atkins Inorganic chemistry, Oxford university press. Cotton, Wilkinson, Murillo, Bachmann Advanced Inorganic Chemistry Wiley India Pvt.Ltd 3.B.Douglas, D.MeDaniel and J.Alexander Concepts and models of Inorganic Chemistry IIIrd Edition. John Wiley & sons, Inc 4.S.J Lippard and J.M Berg. Principles of Bioinorganic chemistry University Science Books, California. 5.David E.Fenton, Bio coordination Chemistry Oxford University press. 6.I Bertini, H.B.Grey, S.J.Lippard and J.S Valentine, Bioinorganic Chemistry Viva Books Pvt Ltd, New Delhi. 7.DMP Mingos, Essential Trends in Inorganic Chemistry Oxford University Press. 8.Indrajeet Kumar Organometallic compounds Pragati Prakasan,Meerut

IIYEAR-III Semester SUBJECT CODE: 3.3 SUBJECT: PHYSICAL CHEMISTRY III UNIT 1

Reaction Kinetics 1 Review of basic principles: Complex reactions- Reversible, parallel, consecutive and branching reactions- Principles of microscopic reversibility. Theories of reaction rate: collision theory steric factor- potential energy surfaces- transition state theory- Eyring equation- comparison of two theories- Thermodynamic formulation of reaction ratessignificance of G#, H # and S # volume of activation- Effect of pressure and volume on the velocity gas reaction Unimolecular reaction- Lindman- Hinshelwood mechanism and RRKM theories- Fast reaction relaxation, flow method- flash photolysis- Magnetic and Resonance method. Theoretical calculation of energy of activation- soling problem involving Ea, E, H and S.

UNIT II

Reaction Kinetics II Chain reaction stationary and non stationary chain-explosion and explosion limits- free radical and chain reaction- steady state treatment- kinetics of H2-CI2 and H2-Br2decomposition of acetaldehydeRice Herzfeld mechanism- Branching chain- H2O2 reaction- Semenov Hinshelwood mechanism of explosive reaction.

UNIT III

Catalysis and Chemical Kinetics: Acid-base catalysis- specific and general catalysis- prototropic and protolytic mechanism- examplesAcidity function.Enzyme catalysis- Michaelis-Menten equation- derivationeffect of pH and temperature. Reaction in solution- Factors determining reaction rates in solution Effect of pressure- dielectric constant- ionic strength- cage effect- Bronsted Bjerrum equation- Primary and secondary kinetic salt effect- Influence of solvent on reaction rate- Hammet & Taft equation.

UNIT IV Surface chemistry: Different types of surfaces- Thermodynamics of surfaces- Gibbs adsorption equation and its vertification- surfaces actants and micelles- surface film- surface pressure and surface potential and their measurements and interpretation- Application of Low energy electronDiffraction and photoelectron- ESCA and Auger Spectroscopy to the study of surfaces. Adsorption- Langmuir adsorption isotherm- Kinetic and statistical derivationMulti layer adsorptionDifferent types- BET theory and Harlein- Jura theory Measurement of surface area of solids using Langmuir, BET and Harlein-Jura isotherm- Heat of adsorption- adsorption isosters and determination of heat of adsorption- Langmuir adsorption isotherm applied to rate laws for surface catalyzed reaction- The Eleyideal mechanism flash desorption.

UNIT V Colloids: Structure and stability of colloids, Micelles The electrical double layer- Eletro kinetic phenomenazeta potential- electro osmosis- colloids- zeta potential (derivation)- sedimentation potential- streaming potential- donnan membrane equilibrium- Macromolecules- different averagesMethods of molecular mass determination Osmotic method- sedimentation methods- light scattering methods. REFERENCE K.J. Laidler-Chemical kinetics Pearson Education S. Glasstone, K.J. Laidler and Eyring- The Theory of rate processes- Mc Graw Hills J. Rajaram and J.C. Kuriacose- Kinetics and Mechanism of chemical transformations- Mac Millan India Ltd Alberty and Silbey- Physical chemistry- Wiley G.K. Vemulappally- Physical chemistry- Prentice Hall of India P.W. Atkins- Physical chemistry- Oxford University press A.W.Adamson- The physical chemistry of surfaces- 4th edition- Wiley 1982 Alexander and Johnson- Colloid science- Oxford University Press Gavariker- Polymer science New age International publishers

SUBJECT CODE: 3.4 SUBJECT: COMPUTIONAL CHEMISTRY

UNIT I

Molecular mechanics Perspective- basic principles-Developing force field- The stretch energy- The bending energy- The torsional energy- The Vander walls energy- The electrostatic energy- Cross terms- Parametrising the force field- Calculation using the force field - Geometries and energies of Small to medium sized molecules- Polymers- transition states-MM in organic synthesis-Molecular mechanics and Monte Carlo simulations- Geometries and frequencies calculated by MM -Strength and weakness of MM-Hybrid force field Electronic structure methods.

UNIT II

Introduction of Quantum mechanics in Computational ChemistryPerspective- The development of quantum mechanics-The Born Oppenheimer approximationSchrdinger equation- Koopmans theorem- Restricted and unrestricted Hartree- Fock modelsApplication of the Schrdinger equation to chemistry by Huckel- Hybridisationmatrices and determinants- simple Huckel theory-Application-The nodal properties of MOs Stability indicated by energy levels and aromaticity. Extended Huckel method.

UNIT III

Abinitio Calculation Perspective- The basic principles of the abinitio method. Approximation methods- Self-Consistent field theory- The energy of a Slater determinant- Hartree- Fock equation- Basis setsSlater and Guassian type orbitals-Classification of basic sets- Minimum basis set- Split valencediffused and polarization and correlation consistent basis sets- post HF calculation- ApplicationGeometry optimization ,Frequency calculation and transition state optimization of simple systemsStrength and weaknessConfiguration interaction, Moller- plesset perturbation theory and Coupled cluster methods(qualitative study only)- -

UNIT IV

Semi Empirical Method Perspective-The basic principle of SCF-SE methods- Neglet of diatomic differential overlap approximation(NDDO)- Intermediate Neglet of differential overlap approximation(INDO)Complete Neglet of differential overlap approximation(CNDO)Parameterization- Modified Intermediate Neglet of differential overlap (MINDO)-Modified NDDO &MNDO models- Austin model1(AM1) application- Geometry optimization ,Frequency calculation and transition state

optimization of simple systems Strength and weakness

UNIT V

Density Functional Calculation

Basic principle Orbital free density functional theory- Kohn-sham theory Reduced density matrix methods-Local density approximation application- Higher ordergradient or meta-GGA methods-Hybrid or hyper-GGA methods- Performance and properties of density functional methods- Geometry optimization ,Frequency calculation and transition state optimization of simple systems- Strength and weakness.

REFERENCES: Errol Lewars Computational Chemistry: Introduction to the Theory and Applications of Molecular and Quantum Mechanics Spriger India I.N Levine Quantum Chemistry, Prentice Hall of India Vth edition Tamas Veszpremi and Miklos Feher Quantum Chemistry: Fundamentals to applications Springer India David C Young, Computational Chemistry:. A Practical Guide for Applying Techniques to Real World Problems Wiley Interscence P.W. Atkins, Molecular Quantum Mechanics. Oxford University Press G. H. Grant and W. G. Richards Computational Chemistry Oxford University Press

SUBJECT CODE: 3.5 SUBJECT: PRACTICAL III- PHYSICAL CHEMISTRY Conduct metric titrations: 1 NH4cl-NaOH 2 NH4cl-NaOH 3 CH3cooNa-Hcl givesn) 4 Precipitation titration Kcl-AgNo3- (Kcl-Ki mixture) 5 Determination of dissociation constant of Weak acid 6 Heat of solution by solubility method Potentiometer 7 Redox titrations 8 Fc2 - cerci Fe2+ 9 Fe2+ - ceric-Fe2+ 10 CI Ag cl +I 11 Dissociation constant of week acid 12 solubility product by chemical cell and concentration cell 13 Adsorption of Oxalic acid / acetic acid on charcoal. KI Kmno4 KI - (NH4cl +Hcl) - (Hcl+ CH3 COOH) - Buffer CCH3COOna +CH3COOH (Na OH strength

IIYEAR-IV Semester SUBJECT CODE: 4.1 SUBJECT: PRINCIPLES OF ANALYSICAL CHEMISTRY

1. Chemical Instrumentation : Elementary Electronics, Simple integrated circuit, Semiconductor, Power supply, transformer, operational amplifier, Detectors (Oscilloscope and recorders), transducers, Rectifiers, Signal to noise ratio, Electronic components (Resistors, capacitors, inductors,

transistors), Measuring instruments for pressure, temperature, pH, speed, flow, current and voltage. 2. Acid Base Equilibria : General concept of acid-base equilibria in water and in non-aqueous solvent, Definition of pH and pH scale (Srenson and operational definitions), and its significance, Hammett acidity function, pH calculation for aqueous solutions of very weak acid and very weak base, salts of weak acid and weak bases, mixture of weak acid and its salts, mixture of weak base and its salts, polybasic acids and their salts, polyamines and amino acid, comparison of solution of polybasic acid as a function of pH, protolysis curves. 3. Buffer Solutions : Theory of buffer solution, dilution and salts effects on the pH of a buffer, Buffer index, Criteria and expression of maximum buffer capacity, Application of pH buffers, Preparation of buffer solutions of known ionic strength (Typical examples). Practical limitations in use of buffers, Metal ion buffers and their applications, Biological buffers and their applications. 4. Photometric Titrations : Basic principles, comparison with other titrimetric procedures, types of photometric titration curves, Instrumentation (Titration

cell, Detectors, choice of analytical wavelength). Quantitative applications, Typical examples of one component and multicompo-nent analyses. Books Recommended 1. D.A. Skoog and D.M. West, Fundamental of Analytical Chemistry, International Edition, 7th Edition (1996), Saunders College Publishing, Philadelphia, Holt, London. 2. R.L. Pecsok, L.D. Shields, T. Cairns and L.C. McWilliam, Modern Methods of Chemical Analysis, 2
nd

(1976), John Wiley & Sons, New York.

3. D.A. Skoog, Principles of Instrumental Analysis, 5 Edition (1998), Saunders College of Publishing, Philadelphia, London. 4. H.A. Strobel, Chemical Instrumentation: A Schematic Approach, 2 (1973), Addison Wesley, Reading, Mass. Additional References 1. H.A. Laittnen and W.E. Harris, Chemical Analysis, 2 Edition (1960), McGraw Hill, New York. 2. R.G. Bates, Electrometric pH Determinations: Theory and Practice, 3rd Edition (1973), John Wiley & Sons, New York. 3. G.D. Moody and J.D.R. Thomas, Ion-selective Electrodes, London. 4. G.W. Ewing, Instrumental Methods of Chemical Analysis, 5 Edition (1978), McGraw Hill Book Co., New York.
th nd nd

th

Edition

International Student

IIYEAR-IV Semester SUBJECT CODE: 4.2 SUBJECT: SURFACE CHEMISTRY

Unit I: Adsorption and surface phenomenon:

Physisorption and chemisorption , adsorption isotherms, Langmuir and B. E. T. equation and significance in surface area determination, surface films, states of insoluble films, L. B. films and their application, adsorption from solution, adsorption types, surface excess concentration , Gibb's adsorption equation : derivation , significance and experimental verification , catalytic activity of surfaces.

Unit II: Micelle

Surface activity, surface active agents and their classification, micellisation, critical micelle concentration ( cmc) thermodynamics of micellisation , factors affecting cmc, methods of determination of cmc , reverse micelle , solubisation of water insoluble organic substances , use of surfactants in oil recovery ,

Unit III: Emulsion

Types of emulsion, theories of emulsion and emulsion stability, identification of emulsion types, inversion emulsion, microemulsion : theory and application ,

Unit IV: Liquid gas and liquid interfaces Surface tension, capillary action, methods of determination of surface tension, surface tension across curved surfaces, vapor pressure of droplet ( Kelvin equation) , surface spreading , spreading coefficient, cohesion and adhesion energy,contact angle, constant angle hystereis, wetting and detergency.

Unit V : Solid - Solid interfaces

Surface energy of solids, adhesion and adsorption, sintering and sintering mechanism, Tammann temperature and its importance, surface structure and surface composition.

REFFERNCE BOOKS 1. Physical chemistry of surfaces: A. W. Adamson. 2. Theory of adsorption and catalysis by Alfred Clark , 3. Chemisorption by B. M. W. Trapnell and H.O. Hayward. 4. Introduction to colloide and surface chemistry by D. J. Shaw. 5. Theories of chemical reaction rates by A. J. K. laidler 6. Surface chemistry by J. J. Bikermann

IIYEAR-IV Semester SUBJECT CODE: 4.3 SUBJECT: OF CHEMISTRY MATERIALS Unit I: Glasses, Ceramics, Composite and Nanomaterials

Glassy state, glass formers and glass modifiers, applications, Ceramic structures,mechanical properties, clay products. Reformatories, characterizations, properties and applications.Microscopic composites; dispersion - strengthened and particle - reinforced, fibre -reinforced composites, macroscopic composites. Nanocrystline phase, preparation procedures, special properties, and applications.

Unit II: High Tc Materials

Defect perovskites, high Tc superconductivity in cuprates, preparation and characterization of 1-2-3 and 2-1-4 materials, and normal state properties; anisotropy; temperature dependence of electrical resistance; optical photon modes,superconducting state; heat capacity; coherence length, elastic constants, position lifetimes, microwave absorption - pairing and multigap structure in high Tc materials , applications of high Tc materials.

Unit III: Polymeric Materials

Molecular shape , structure and configuration, crystallinity, stress- strain behavior,thermal behavior , polymer types and their applications, conducting and ferro -electric polymers.

Unit IV

a)Thin films and Langmuir- Blodgett Films Preparation techniques; evaporation / sputtering, chemical processes, MOCVD, sol - gel etc. Langmuir- Blodgett (LB) film, growth techniques, photolithography, properties and application of thin and LB films.

b) Materials of Solid Devices Rectifiers, transistors, capacitors IV-V compounds, low dimensional quantum structure; optical properties.

REFFERNCE BOOKS 1. Solid State Physics, N. W. Ashcrott and N. D. Mermin, Saunders College 2. Material Science and Engineering, An introduction , W. D. Callister, Willey. 3. Principals of Solid State, H. V. keer, Willey Eastorn. 4. Materials Science , J. C. Anderson , K. D. Leaver, J. M. Alexander and R. D. Rawlings, ELBS 5. Thermotropic Liquid Crystals, Ed, G. W. Gray, John Willey. 6. Text book of liquid crystals, Kelkar and Halz , Chemie Verlag