File: Chem(M) Syl-2007-2008 DEPARTMENT OF CHEMISTRY FACULTY OF SCIENCE THE UNIVERSITY OF RAJSHAHI Syllabus for The Degree of Master of Science (M. Sc.) in Chemistry Session: 2007-2008 Examination 2008 2 PHYSICAL CHEMISTRY BRANCH: Courses Chem 511F Chem 512F Chem 513F Chem 514F Chem 515F Chem 516F Chem 517F Chem 511AH Chem 511VH* Chem 511L** Course Titles Electrolyte solutions and Electrode Processes Advanced Chemical Kinetics Polymer Chemistry Bio-Physical Chemistry Physical Methods in Chemical Analysis Electroanalytical Chemistry Theoretical Chemistry-III Class Assessment –V Viva-voce–V Physical Chemistry Practical –V Units 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.5 0.5 2 Credits 4 4 4 4 4 4 4 2 2 8 Marks 100 100 100 100 100 100 100 50 50 200 8.0 32 800 OR Chem 599*** Thesis / Dissertation on topics of Physical Chemistry Total Credit Courses available Students shall have to choose any five full unit theoretical courses from first seven full unit theoretical courses (Chem 511 F – Chem 517 F) * Viva-voce examination includes the assessment of the students through oral examination of all the courses. ** Laboratory courses include 30% (60) marks for continuous Lab. assessment. *** Thesis includes 30% (60) marks for oral examination on the thesis. Examination of the theory courses of 100 marks (1.0 unit, 4 credits) shall be of 4 (four) hours duration, and of the practical courses of 200 marks (2.0 unit, 8 credits) shall be of 24 (twenty four) hours duration (4 days). The students shall submit a report after each Lab. class to the Lab. teacher(s) for evaluation. After evaluation the report shall be returned to the students. The lab. teacher(s) shall submit the average marks of all Lab. evaluations in sealed envelopes to the chairman of the relevant examination committee within three weeks from the last lab. held. The class assessment course includes tutorial, terminal, home assignment, and /or class examinations taken on theoretical courses by the relevant course teacher(s) during the academic year. The class teacher(s) of each course shall submit the average consolidated marks of class assessments in sealed envelope to the Chairman of the relevant examination committee within three weeks from the last class held. The examination committee shall send a copy of the consolidated marks for each of the viva-voce examination, class assessment, lab. evaluation and practical examinations to the controller of examinations No student having less than 60% class attendance shall be allowed to sit for the examination. Course: Chem 511F Electrolyte solutions and Electrode Processes Examination: 4 Hours Full Marks : 100 (1 unit, 4 credits) (80 lectures, 4 lectures per week) 1. Structure and properties of electrolyte solutions (15 lectures): Structure and properties of water; intermolecular forces; solubilization process; solvation of ions – theories and energetics, determination of solvation number; Debye-Hückel theory of ion-ion interactions in electrolyte solutions, critical appreciation of Debye-Hückel theory; modification of Debye-Hückel theory; activity coefficient and methods for its determination; theory of ion association, ion association equilibrium. Diffusion in electrolyte solutions: Fick’s laws, application of Fick’s laws to electrolyte solutions, ion-ion interaction during diffusion of electrolytes, diffusion potential. 2. Interfacial electrochemistry (20 lectures): Origin and thermodynamics of electrode potential: potential differences in electrochemical systems, electromotive force and electrode potentials as the sum of Volta potentials, the nature of potential differences across phase boundaries, the Nernst osmotic theory and the hydration theory of electrode potentials. Theories of double layer formation at the electrode-solution interfaces: formation of the double layer; the parallel plate condenser theory (Helmholtz double layer), the diffuse layer theory (Gouy-Chapman double layer), the adsorption theory (Setern’s treatment) of the double layer; recent developments in double layer theory. Adsorption at electrode surfaces: isotherms and the behaviour of reactant ions and molecules at electrodes – Langmuir isotherm, Temkin isotherm and heterogeneity of interaction effects, electrochemical isotherms for ion adsorption. 3. Kinetics of electrode processes (15 lectures): Electrode polarization and overpotential; classification of polarization phenomenon, the concept and theory of diffusion overpotential; diffusion-controlled reactions; principles and applications of polarography; basic factors in ion discharge; formulation of overall kinetic rate equation, concentration dependence of rate of a discharge step, net currents and exchange currents; heats of activation and frequency factors; activation controlled reactions; kinetics and mechanism of some simple electrode reactions, viz., hydrogen evolution at the cathode and oxygen evolution at the anode. 4. Some electrochemical systems of technological importance (10 lectures): Corrosion and passivation of metals, corrosion testing, corrosion industries, theories of corrosion and methods of combating corrosion; electrochemical energy conversion devices, primary and secondary batteries, fuel cells, electroplating of metals, viz., Cu, Ni, and Cr; factors governing the nature of deposits; ornamental and porous deposits 5. Organic reactions at electrodes (20 lectures): The Electrolysis Cell; choice of working and reference electrodes; selection of solvent and supporting electrolyte. Reduction of functional groups: carbonyl compounds, nitro groups, carbon-halogen bonds, unsaturated compounds, carbon-nitrogen bonds, organosulfur compounds, organometallic compounds, peroxides, reduction of carbon-nitrogen single () bonds. Oxidation of functional groups: the Kolbe reaction, mechanism and role in organic synthesis, oxidation of unsaturated compounds, anodic substitution, alkoxylation, acetoxylation, cyanation and acetamidation; oxidation of aromatic alcohols, anhydrides; oxidation of olefins; anodic halogenation. Electrosynthesis of some compounds of commercial importance: propylene oxide, hydroquinone, adiponitrile, tetraethyl lead etc. 3 Books Recommended: 1. D. Eisenberg and W. Kauzmann 2. J.O’M. Bockris and A.K.N. Reddy 3. B.E. Conway 4. K.J. Vetter 5. G. Khortum 6. L. Anthrpov 7. W. Blum and G.B. Hogaboom 8. Kohler and Creighton 9. Mars G. Fontans and Greene 10. S.N. Banerjee 11. E. C. Potter 12. G. Mantell 13. M.R. Rifi and Frank H. Covitz 14. Demetrios K. Kyriacou : : : : : : : : : : : : : : The Structure and Properties of Water Introduction to Electrochemistry Electrode Processes Electrochemical Kinetics Treatise on Electrochemistry Theoretical Electrochemistry Principles of Electroplating and Electroforming Electrochemistry – Principles and Applications Corrosion Engineering An Introduction to the Science of Corrosion and Its Inhibition Electrochemistry – Principles and Applications Industrial Electrochemistry Introduction to Organic Electrochemistry Basics of Electro-organic Synthesis Course : Chem 512F Advanced Chemical Kinetics Examination : 4 Hours Full Marks : 100 (1 unit, 4 credit) (80 lectures, 4 lectures per week) 1. Energy of activation (20 lectures): Statistical distribution of molecular energies: simple statistical expressions; Tolman’s theorem. Potential energy surfaces: ab initio calculations of potential energy surfaces: treatments based on London equation, variational calculations; semiempirical calculations of potential energy surfaces: London-Eyring-Polanyi (LEP) method, Sato method, modified LEP methods, bond-energy-bond-order (BEBO) method; empirical treatments of activation energy. 2. Theories of reaction rates (10 lectures): Conventional transition state theory (STST); derivations of rate equation from CTST; symmetry numbers and statistical factors; applications of CTST to reaction between atoms and reactions between molecules with a few specific examples (e.g., the reaction H + HBr = H 2 + Br2); thermodynamic formulation of CTST; assumptions and limitations of CTST; multiple crossing and the equilibrium hypothesis; reparability of the reaction coordinate; quantum effects; extensions of transition state theory; variational transitional-state theory; quantum-mechanical transition-state theory; microscopic reversibility and detailed balance. 3. Theory of unimolecular reactions (10 lectures): Recapitulation of Lindemann-Christiansen and Hinshelwood’s treatments. The Rice-Ramsperger-Kassel (RRK) treatment, Slater’s treatment, Marcus’s extension of RRK treatment (RRKM); influences of foreign gases; intramolecular and intermolecular energy transfer; laser-induced unimolecular reactions; decomposition of ions; combination and disproportionation reactions; mechanism of atom and radical combinations. 4. Reactions in solution (20 lectures): Effects of solvents on reaction rates; factors determining reaction rates in solution; collision theory in solutions; transition-state theory for reactions in solution: influence of internal pressure of the solvent, influence of solvation of reactants and activated complex; reaction between ions: influence of solvent dielectric constant on rates, pre-exponential factors of ionic reactions, single-sphere activated complex for activated complex, influence of ionic strength, more advanced treatments for ionic reactions in solutions; ion-dipole and dipole-dipole reactions in solutions; influence of hydrostatic pressure on rates; substituent and correlation effects on rates; diffusion controlled reactions: full microscopic diffusion control and partial microscopic diffusion control, reactions involving two ions. 5. Composite reactions (10 lectures): Rate equations for composite mechanisms: simultaneous and consecutive reactions, ratedetermining steps, microscopic reversibility and detailed balance; chain reactions; some inorganic reaction mechanisms: hydrogen-bromine reaction, hydrogen-chlorine reaction, hydrogen-iodine reaction, comparison of hydrogen-halogen reactions formation and decomposition of phosgene, decomposition of nitrogen pentoxide, decomposition of ozone, paraortho hydrogen conversion; mechanism of organic decomposition reactions: Goldfinger-Letort-Niclause rules, molecular processes, decomposition of ethane and acetaldehyde, inhibition mechanisms; mechanism of gas-phase combustion of hydrogen and hydrocarbons. 6. Reaction dynamics (10 lectures): Importance of reaction dynamics; molecular-dynamical calculations of chemical reactions: the reaction H + H2, the reaction Br + H2 and more complex reactions; chemiluminesence; features of potential energy surfaces: attractive surfaces for exothermic reactions, repulsive surfaces for exothermic reactions, surfaces of intermediate types for exothermic reactions, selective enhancement of reaction, disposal of excess energy, gradual and sudden surfaces, influence of rotational energy; molecular beams: stripping and rebound mechanisms, state-to-state kinetics. Books Recommended: 1. P. W. Atkins : Physical Chemistry 2. Keith J. Laidler : Chemical Kinetics 3. S. Glasstone, K.J. Laidler & H. Eyring : The Theory of Rate Processes 4. K.J. Laidler and J.H. Meiser : Physical Chemistry Course: Chem 513 F Polymer Chemistry Examination : 4 hours Full Marks : 100 (1 unit, 4 credits) (80 lectures, 4 lectures per week) 1. Basic concepts of polymers (10 lectures): Macromolecules; Repeating units of polymers; Monomer; Representation of polymer structures; End groups in polymer chains; History of polymers; Classification of polymers; Polymer nomenclature; Linear, branched and cross linked polymers; Conditions of polymerization; Molar masses and their distribution; Comparison of addition and condensation polymers; Basic ideas of thermoplastics, thermosets, elastomers, fibres and plastics; Isomerisation in polymers; Utility of polymers. 4 2. Condensation polymerization (12 lectures): Definition; Types of polycondensation reactions; Kinetics of condensation or step-growth polymerization; Degree of polymerization and extent of reaction; Carothers equation for bifunctional polymers: Molar mass distribution in linear condensation polymerisation; Factors influencing the maximum attainable molar mass of condensation polymers; Techniques of condensation polymerization; Branched and crosslinked condensation polymers. 3. Addition polymerization (18 lectures): Definition; Types of addition polymerization (free-radical, cationic, anionic and coordination); Monomers and initiators; Effect of substituents on the polymerization mechanism of vinyl polymers; Overall scheme of free-radical polymerization: Methods of radical production; Efficiency of initiators; Chain propagation, chain transfer and chain termination; Kinetics of free radical polymerization; Average kinetic chain length and average degree of polymerization; Chain transfer and its effects on ideal free radical polymerization; Chain transfer constant; Initiation and retardation; Techniques of free radical polymerization. Ionic and coordination polymerization: Mechanism of anionic polymerization; Living polymers; Mechanism of cationic polymerization; Mechanism of coordination polymerization; Ring opening polymerization; Comparison of coordination and addition polymerization. 4. Copolymerization (12 lectures): Copolymerization types (block, random and graft copolymerizations); Simple copolymer equation (kinetics and mechanism of binary free radical copolymerization); Monomer reactivity ratios; Significance and determination; Copolymerization behaviour and reactivity ratio; Q-e scheme; Reactivities of radicals and monomers: Resonance effects, polar effects, steric effect; Effect of reaction condition (temperature, pressure, medium, complex formation); Rates of free radical copolymerization; Ionic copolymerization; Copolycondensation; Technical significance of copolymerization; Important copolymers. 5. Rheology of polymers (10 lectures): Mechanical behavior of polymers; Stress and strain; Ideal elastic solid (Hookian model); Ideal fluid (Newton or dash pot model); Maxwell model for viscoelasticity ; Voigt model for viscoelascity; deformation behaviour of polymeric materials; Non-Newtonian fluid; Stress relaxation; Increase of strain under constant stress; Rheological measurements; Hysteresis. 6. Structure-property relation of polymers (10 lectures): Crystallinity of polymers; Factors influencing the formation of crystallite in polymers, Change of polymer property at crystalline melting point; Factors influencing the crystalline melting point; Orientation of crystalline polymers; Size of crystallite and degree of crystallinity; Glass transition in polymers. 7. Molar mass, shape and size of polymers (8 lectures): Determination of molar mass of polymers by light scattering, colligative properties, end group analysis, ultracentrifuge and viscosity methods; Shapes of linear chain polymers in solution; Shapes of polymers molecules and viscosity; Effect of concentration, temperature and solvent on viscosity of polymer solutions. Recommended Books: 1. Alfred Rudin : The elements of Polymer Science and Technology 2. George Odian : Principles of Polymerization 3. Premamoy Ghosh : Polymer Science and Technology of Plastics and Rubbers 4. Paul C. Hiemenz : Polymer Chemistry the Basic Concepts 5. P.J. Flory : Principles of Polymer Chemistry Course : Chem 514F Biophysical Chemistry Examination: 4 hours Full marks : 100 (1 unit, 4 credits) (80 lectures, 4 lectures per week) 1. Noncovalent bonding and pH buffering (10 lectures): Water the biological solvent, stabilizing and organizing forces of nature, acid base equilibria, principle of pH buffering, buffering of blood, laboratory use of buffers, ionic strength.. 2. Biomolecules (12 lectures): Building block molecules of biomolecules, amino acid structures, polypeptides, ionic properties of amino acids and polypeptides, nucleotides and nucleic acids, base composition and base sequence of nucleic acids, simple idea about carbohydrates and lipids. 3. Proteins (15 lectures): Classifications, primary, secondary, tertiary and quarternary structure of globular proteins, salting in and salting out of proteins, chemistry of ion exchange and chromatographic technique in isolation/purification of protein characterization of proteins, molecular weight determination of proteins by PAGE and get filtration techniques. Proteins binding and phermercodynamics, complexation and drug action, metal complexation in biological systems. 4. Enzymes (15 lectures): Nomenclature, cofactor, principle of catalysis, enzyme catalyzed reactions having one substrate, MM equation, Km and Vm values determination, pH and temperature effects on catalysis, competitive, non-competitive and uncompetitive inhibition of catalysis. Cooperative binding, quantitative cooperative binding by Hill plot. Allosteric inter action, oxygen binding of myoglobin and hemoglobin . 5. Bioenergetics (20 lectures): ATP and its role in bioenergetics, control points in metabolic pathways, carbohydrate metabolism, the energetic of the citric acid cycle, lipid metabolism, oxidative phosphorylation, nitrogen metabolism. 6. Biological membrane ( 8 Lectures): Structure and function of biological membrane, diffusion, active and passive transport, Donnan effect, Na+-K+ pump. Recommended Books: 1. R.C. Bohinski : Modern Concepts of Biochemistry 2. G. Zubay : Biochemistry 3. R.K. Murray et. al. : Harper’s Biochemistry 4. R.K. Scopes : Protein Purification 5. C.N. Price & R.A. Dwek : Principles and Problems in Physical Chemistry for Biochemists. 6. D. Eisenberg & D. Crothers : Physical Chemistry with Applications to the life Sciences. 7. I. Tinoco et. al. : Physical chemistry: Principles and application in Biological sciences. 8. C.A. Cantor & P.R. Schimmel : Biophysical chemistry Part 1, 2 & 3. 9. A. Martin et. al. : Physical Pharmacy 10. W.H. Elliott & D.C. Elliott : Biochemistry and molecular biology. 5 Course : Chem 515F Physical Methods in Chemical Analysis Examination : 4 Hours Full Marks : 100 (1 unit, 4 credits) (80 lectures, 4 lectures per week) 1. (a) Ultraviolet and Visible absorption spectroscopy ( 6 lectures): Components of instrument, applications to qualitative and quantitative analysis, photometric titrations (b) Optical rotatory dispersion (ORD) and circular dichroism (CD) (10 lectures): Optical activity and circularly polarized light; parameters for optical activity; measurement of ORD and CD; physical basis of optical activity; optically active chromophores; the use of CD to determine secondary structures. 2. Atomic absorption spectroscopy (8 lectures) : Theory, instrumentation and applications. 3. Fluorescence spectroscopy (8 lectures) : Transition probabilities and lifetime, quantum yield, fluorescence intensity and polarization, fluorophores and fluorescence probes, fluorescence parameters, molecular dynamics study. 4. (a) Infrared spectroscopy (5 lectures) : Instrument components, sample handling, qualitative and quantitative applications, far infrared spectroscopy. (b) Raman Spectroscopy (8 lectures) : Classical and quantum theory of Raman spectroscopy, rotational Raman spectrum, instrumentation, effect of nuclear spin, vibrational Raman spectra, polarization of Raman lines, determination of structure by Raman spectra, vibrational-rotational Raman spectra. 5. (a) NMR spectroscopy (12 lectures): 13C, 19F, 14N, 15N, 31P and 2H NMR spectroscopy. Multiple pulse NMR experiments, some two-dimensional NMR experiments, CIDNP experiments, application of NMR in quantitative analysis in multicomponent mixtures, hydrogen bonding, keto-enol tautomerism, intermolecular conversion and exchange effects. (b) Electron spin (paramagnetic) resonance spectroscopy (ESR / EPR) (8 lectures) : Principles, instrumentation, hyperfine structure, radicals, anions of aromatic hydrocarbons, relation between hyperfine-splitting and unpaired electron density, ESR spectra of transition metal complexes, applications. 6. Mossbauer spectroscopy (5 lectures) : Principle, instrumentation, factors affecting the spectra and applications. 7 Chromatography (10 lectures) : Principles, instrumentations and applications of HPLC and GC. Books recommended: 1. J.C. Miller & J.N. Miller : 2. W.L. Masterton & E.J. Slowinski : 3. D.A. Skoog et. al. : 4. D.C. Harris : 5. R.D. Braun & F.H. Walters : 6. D.A. Skoog : 7. I.D. Campbell & R.A. Dwek : 8. Dr. B.K. Sharma : 9. P.E. Pfeffer & W.V. Gerasimowicz : 10. J.K.M. Sanders & B.K. Hunter : 11. H.H. Mantsch et. al. : 12. E.L. Johnson & R. Stevenson : Statistics for Analytical Chemistry Elementary Mathematical Preparation for General Chemistry Fundamentals of Analytical Chemistry Quantitative Chemical Analysis Applications of Chemical Analysis Principles of Instrumental Analysis Biological Spectroscopy Instrumental Methods of Chemical Analysis NMR in Agriculture Modern NMR Spectroscopy DMR, Application in Chemistry, Physics and Biology in Progress in NMR Spectroscopy, 1977, Vol. 11, Part-4, PP 211-271. Basic Liquid Chromatography. Course : Chem 516F Electroanalytical Chemistry Examination : 4 Hours Full Marks : 100 (1 unit, 4 credits) (80 lectures, 4 lectures per week) 1. Fundamental Electroanalytical Concepts (5 lectures): Faradaic processes: mass transport-controlled reactions, potential step and potential sweep experiments, reactions controlled by the rate of electron transfer, coupled chemical reactions. 2. Elecrode Reactions in Cyclic Voltammetry (15 lectures): Cyclic voltammetry, data interpretation, reversible, irrerversible and quasi-reversible systems, reaction mechanisms, and adsorption processes, quantitative aplications. Scanning Probe Microscopy: Scanning tunneling microscopy, atomic force microscopy (AFM), scanning electrochemical microscopy, electrochemical quartz crystal microbalance (EQCM). 3. Controlled Potential Techniques of Voltammetry (15 lectures): (a) Chronoamperometry, pulse voltammetry: normal pulse, differential pulse, squarewave, and stair case voltammetry. (b) Stripping and flow analyses: Stripping analysis: Anodic, potentiometric and adsorptive voltammetry and potentiometry, cathodic stripping voltammetry and its applications. Flow analysis: principles, cell design, mass transport and current response, detection modes. 4. Electrodes of Electrochemical Cells (15 lectures): Solvent and supporting electrolytes, oxygen removal, instrumentation working electrods viz, mercury elecrodes; solid electrodes, rotating disk electrodes, carbon electrodes: glassy-carbon, carbonpaste and carbon-fiber electrodes, metal electrodes, chemically modified electrodes: self-assembled monolayers, sol-gel encapsulation of reactive species, electrocatalytic modified electrode, preconcentrating electrodes, permselective coatings, conducting polymers, microelectrodes: diffusion at microelectrodes, configurations of microelectrodes, composite electrodes. 6 5. Potentiometry (15 lectures): Principles of on line & in-vivo potentiometric measurements using, ion selective electrodes, glass electrodes, pH electrodes, glass electrodes for other cations, liquid membrane electrodes, electrodes, solid state electrodes, coated wire electrodes. 6. Electrochemical Sensors (15 lectures): Biosensors (enzyme-based electrodes), impractical and theoretical considerations, enzyme electrodes of analytical significance e.g. glucose sensors, ethanol and urea electrodes, toxin (enzyme inhibition) biosensors, tissue and bacteria electrodes. Affinity biosensors (immunosensors, DNA hybridization biosensors, receptor based sensors), gas sensors: carbon dioxide sensors, oxygen electrodes, solid-state devices: microfabrication of solid state sensor assemblies, microfabrication techniques, sensor arrays. Recommended Books: 1. Joseph Wang 2. A.J. Bard. 3 Peter T. Kissenger & William R. Heineman 4. Royce W. Murray 5. A.E.G. Cass 6. J.J. Lingane 7. Fred C. Anson : : : : : : : Analytical Electrochemistry Electrochemical Methods: Fundamentals and Applications Laboratory Techniques in Electroanalytical Chemistry. Molecular Design of Electrode Surfaces Biosensors Electroanalytical Chemistry Electroanalytical Chemistry Course : Chem 517F Theoretical Chemistry-III Examination : 4 Hours Full Marks : 100 (1 unit, 4 credits) (80 lectures, 4 lectures per week) 1. Quantum theory of the chemical bond - diatomic molecules (20 lectures): Born-Oppenheimer approximation; nuclear motion in diatomic molecules; the hydrogen molecule ion (H2+); approximate treatments of H2+ ground electronic state; molecular orbitals for H2+ excited states; molecular orbital (MO) configurations of homonuclear diatomic molecules; electronic terms for diatomic molecules; the hydrogen molecule (H 2); valence-bond (VB) treatment of H2; comparison of MO and VB theories; MO and VB wave functions for homonuclear diatomic molecules; excited states of H2; electron probability density; dipole moments; the Hartree-Fock method for molecules; self-consistent-field (SCF) wave functions for diatomic molecules; MO and VB treatments of heteronuclear diatomic molecules; the valence electron approximation; configuration iteration (CI) wave functions. 2. Quantum theory of the chemical bond - polyatomic molecules (20 lectures): Ab inito, density-functional, semiempirical and molecular-mechanics methods; electronic terms of polyatomic molecules; the SCF MO treatment of polyatomic molecules; basis functions; the SCF MO treatment of H2O; population analysis; the molecular electrostatic potential and atomic charges; localized MOs; the SCF MO treatment of methane, ethane, and ethylene; molecular geometry. 3. -electron theory of organic molecules (10 lectures): Hückel MO theory; the use of symmetry for determining Hückel orbitals; cyclic conjugated polyolefins and Hückel’s 4n + 2 rule; aromaticity and antiaromaticity; non-classical structures; heteroatomic molecules; the free electron model of -electron molecules. 4. Statistical Mechanics and quantum statistics (20 lectures): Phase space and the Liouville’s theorem; equipartition of energy. Quantum statistics: Boltzmann statistics, Fermi-Dirac and Bose-Einstein statistics, comparison of the three statistics; quantum statistics of weakly degenerate and strongly degenerate ideal Fermi-Dirac gases, an ideal gas of photons (blackbody radiation); the density matrix; the classical limit from quantum mechanical expression for Q. Statistical thermodynamics of crystalline solids: vibrational spectrum of a monatomic crystal, Einstein and Debye theories of the heat capacity of crystals, lattice dynamics, phonons, and point defects in crystals. Theories of liquids: The theory of significant structures and the Lennard-Jones Devonshire theory. Books recommended: 1. Ira N. Levine : 2. J.N. Murrel, S.F.A. Kettle & J.M. Tedder : 3. P.W. Atkins : 4. Donald A. Mc Quarrie : 5. H. Eyring, J. Walter & G.E. Kimball : 6. R. Anantharaman : 7. A.K. Chandra : 8. Donald A. McQuarrie : 9. S. Glasstone : 10. Donald A. McQuarrie : 11. Gurdeep Raj : Quantum Chemistry Valence Theory Molecular Quantum Mechanics Quantum Chemistry Quantum Chemistry Fundamentals of Quantum Mechanics Introductory Quantum Chemistry Physical Chemistry, A Molecular Approach Theoretical Chemistry Statistical Thermodynamics Advanced Physical Chemistry Course : Chem 511L Physical Chemistry Practical Examination : 24 (Twenty four) hours (4 days) Full Marks: 200 (2 unit, 8 credits) Experiment-140, continuos Lab. assessment-60 [N.B. In addition to the experiments listed below more experiments on physical chemistry may be done subject to the availability of the Lab. facilities.] 1. Determination of the molar mass of a given polymer. 2. Determination of the limit of homogeneous phase in the three component system: chloroform-acetic acid-water. 3. Determination of the rate constant and order of S2O82- in the reaction S2O82-(aq)+29-(aq) 2SO42- +92(S) 7 4. 5. 6. Kinetic studies on the oxidation of ethanedioic acid. Determination of the Avogadro constant. Studies on the substituent effect on reactivity by measuring the rate of base catalysed hydrolysis of methyl benzoate. 7. 8. 9. 10. 11. Determination of the G°, S°, H° & Cp° for the equlibrium reaction I2 + II3-. Determination of the energy of activation for the reaction 5 KBr + KBrO 3 + 2H2SO4 = 3Br2 +3K2SO4 + 3H2O. Studies of adsorption on liquid surfaces by surface tension measurements. Verification of the formula of inorganic big molecules, e.g., KMnO4 , K2Cr2O7 by the ebullioscopic / Cryoscopic methods. Determination of percentage composition of a binary mixture of nonvolatile nonelectrolyte, e.g., urea, glucose by ebullioscopic / Cryoscopic methods. Determination of Vant Hoff factor of an electrolyte by ebullioscopic / Cryoscopic methods. Determination of the dissociation constant of a weak acid (e.g. acetic acid, oxalic acid etc.) near 100°C/0°C by ebullioscopic / Cryoscopic methods and estimation of pH of the solution. Determination of the hydrolysis constant of a salt conductometrically. Determination of activity coefficient conductometrically. Kinetic studies on the saponification of an ester conductometrically. Determination of the solubility product constant of a suitable salt conductometrically. Determination of the standard oxidation –reduction potential of the Fe2+/Fe3+ system. Determination of the instability constant of the argentamine complex potentiometrically. Determination of the hydrolysis constant of a salt potentiometrically. Determination of the mean activity coefficient of an electrolyte potentiometrically. Determination of the equilibrium constant of Sn4+ + 2 Fe2+ Sn2+ + 2 Fe3+ potentiometrically. Potentiometric titration of a dibasic acid with NaOH and determination of the first and second dissociation constant of the acid. Determination of Isobestic point. Determination of the indicator constant of an indicator. Study of the equlibrium in aqueous solution between ferric nitrate and sodium thiocyanate spectrophotometrically and estimation of stability constant and coordination number of Fe 3+. Determination of the solubility product constant of Cu(II) Iodate spectrophotometrically. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. Recommended Books: 1. D.P. Shoemaker et al 2. G.S. Weiss et al 3 A. Findlay 4. R.C. Das 5. J.N. Gurtu 6. K.K. Sharma 7. J.C. Muhler et al 8. J. Rose 9. J.B. Yadav 10. Newcomb, Wilson et al 11. Daniels et al 12. Brennan et al 13. S.R. Palit 14. C.D. Hodgman et al 15. R.C. West et al 16. L.A. Lange : : : : : : : : : : : : : : : : Experiment in Physical Chemistry Experiments in General Chemistry Practical Physical Chemistry Experimental Physical Chemistry Advanced Experimental Chemistry An Introduction of Practical Chemistry Introduction to Experimental Chemistry A Textbook of Practical Physical Chemistry Advanced Practical Physical Chemistry Experiments in Physical Chemistry Practical Physical Chemistry Experiments in Physical Chemistry Practical Physical Chemistry Handbook of Chemistry and Physics CRC Handbook of Physics and Chemistry Handbook of Chemistry 8 ORGANIC CHEMISTRY BRANCH: Courses Course Titles Units Credits Marks Chem 521F Organic Reactions & Stereochemistry 1.0 4 100 Chem 522F Synthetic Organic Chemistry 1.0 4 100 Chem 523F Advanced Organic Spectroscopy 1.0 4 100 Chem 524F Macromolecular Chemistry 1.0 4 100 Chem 525F* Stereochemistry and Conformations 1.0 4 100 Chem 526F* Advanced Organic Reactions 1.0 4 100 Chem 527F* Bioorganic & Food Chemistry 1.0 4 100 Chem 521AH Class Assessment –V 0.5 2 50 Chem 521VH Viva-voce–V 0.5 2 50 Chem 521L** Organic Chemistry Practical –V 2 8 200 8.0 32 800 OR Chem 599*** Thesis –I (Organic / Industrial) Total Credit Courses available * Any one course shall be chosen out of the three optional courses subject to the approval of the branch. ** Laboratory course include 30% (60) marks for continuous Lab. assessment. *** Thesis includes 30% (60) marks for oral examination on the thesis. Examination of the theory courses of 100 marks (1.0 unit, 4 credits) shall be of 4 (four) hours duration, of 50 marks (0.5 unit, 2 credit) of 2 (two) hours duration and of the practical of 100 marks (1.0 unit, 4 credits) shall be of 12 (twelve) hours duration (2 days). 30% marks of the practical courses are assigned for continuous Lab. assessment. The students shall submit a report after each Lab. class to the Lab. teacher(s) for evaluation. After evaluation the report shall be returned to the students. The Lab. teacher(s) shall submit the average marks of all Lab. evaluation in sealed envelopes to the chairman of the relevant examination committee within three weeks from the last Lab. class held. Class assessment course includes tutorial, terminal, home assignment, and /or class examinations taken on theoretical courses by the relevant course teacher(s) during the academic year. Class assessment comprises (a) 80% marks in tutorial, terminal home assignment and /or class examinations and (b) 20% marks for attendance in the class. The class teacher(s) of each course shall submit the average consolidated marks of class assessments and attendance in sealed envelope to the Chairman of the relevant examination committee within three weeks from the last class held. Viva-voce examination includes the assessment of the students through oral examination of all the courses. No student having less than 60% class attendance shall be allowed to sit for the examination. Course : Chem 521F Organic Reactions & Stereochemistry Examination : 4 hours Full Marks : 100 (80 lectures; 1 Unit; 4 Credits) 1. Free radical Reaction (15 lectures): Stability and structure, generation and fate of free radicals, free radical mechanisms in general: substitution mechanism, mechanism at aromatic substrate, neighboring-group assistance in free radical reactions, reactivity for aliphatic substrates, reactivity at a bridgehead position, reactivity in aromatic substrates, reactivity in the attacking radical, effect of solvent on reactivity. Examples of free radical reactions: (i) hydrogen as leaving group; (ii) allylic halogenation; (iii) halogenation of aldehydes; (iv) substitution by oxygen; (v) hydroxylation at an aromatic carbon and other free radical substitution effected by oxygen 2. Redox reactions : a) Oxidation reactions (10 lectures): Oxidation of alcohols with Cr(VI), with DMSO and DCC, oxidation with PCC, with Jone’s reagent, Collin’s reagent. Allylic oxidation [SeO 2 and Pb(OAc)4]. Peracid and periodate oxidation. Lemieux oxidation, Prevost and Woodward oxidation. b) Reduction reactions (10 lectures): Catalytic hydrogenation, metal hydride reductions, [LiAlH 4, LiAlH(OC4H9)3], B2H6, DIBAL, Na-cyanoborohydirde, reduction with dissolving metals, Birch reduction. 3. Alkylation of active methylene compounds (10 lectures): The formation of enols and enolate anion and their importance, alkylation of relatively active methylene compounds (C-alkylation and O-alkylation), the formation and alkylation of enamines. 4. Protection and interconversion of functional groups (FGI) (15 lectures): Hydroxyl (alcoholic and phenolic), carbonyl, carboxyl, amino and thiol groups. 5. Stereochemistry and conformations (20 lectures) : Stereochemistry, optical activity and chirality, cis-trans isomerism, biological discrimination of enantiomers, enantionmeric excess and optical purity, chirality of conformationally mobile system, conformational analysis, strains, methods of correlation for configurations. ORD, CD. etc. confromation and stereo chemistry of cholesterol, cholestane etc. Recommended Books: 1. Adams et.al. (ed.) 2. H.O. House 3. Carruthers 4. H. Gilman : : : : Organic Reactions (all volumes) Synthetic Application of Organic Reactions Some Modern Methods of Organic Synthesis Advanced Organic Chemistry, (Vol-1 to IV) 9 5. 6. 7. 8. 9. 10. L.F. Fieser and M. Fieser I.L. Finar R.KJ. Mackil & D.M. Smith P. Simpson T.W. Green L.G. Wade; JR : : : : : : Topics in Organic Chemistry Organic Chemistry Vol. 2 A Guidebook to Organic Synthesis Organometallic Chemistry of the Main Group Elements Protective Groups in Organic Synthesis. Organic Chemistry Course: Chem 522F Synthetic Organic Chemistry Examination: 4 hours Full Marks : 100 (80 lectures, 1 unit, 4 credits) 1. Multinuclear aromatic heterocycles (17 lectures): General nature, preparation and properties; Benzo-derivatives of furan, pyrrole, thiophene indole; acridine, phenathridine and diazanaphthalenes. 2. Polycyclic aromatic compounds (17 lectures): General nature, structure, reactions and synthesis of annulenes, twist compounds, cyclophanes, crownethers. 3. Organometallic Chemistry (17 lectures): Organo-copper compounds, organo-zinc compounds, organo-palladium compounds, organo-silicon compounds, organomagnesim and organoselenium compounds, preparation, properties and synthetic uses. 4. Designing organic synthesis (17 lectures): Designing organic synthesis involving one step disconnections: disconnection of simple alcohols, olefins and ketones. Two group disconnections: -Hydroxy carbonyl compounds, , -unsaturated carbonyl compounds and 1,3-dicarbonyl compounds. 5. Synthesis of (12 lectures): a) Agrochemicals: i) Herbicides : Vegadex, Avadex, Eptam and Carbyne ii) Fungicides : Vapam, Nabam and Zineb iii) Insecticides : Sevin and Furadam iv) Pyrifenox : 4-(dichloro metheylene)-2-[N-(ά-methyl benzyl )]-imino-1,2-dithiolane. b) Some important drugs: Salbutamol, trimethoprime, indomethacin, acetazolamide, naproxen and tolmetin sodium. Recommended Books: 1. E.S. Gould 2. R.T. Morison & R.N. Boyd 3. S. Warren 4. P. Simpson 5. A. Kar 6. A. Burger : : : : : : Mechanism and Structure in Organic Chemistry Organic Chemistry Disconnection Approach. Organometallic Chemistry of the Main Group Elements. Medicinal Chemistry Medicinal Chemistry vol. I & II Course: Chem 523F Advanced Organic Spectroscopy Examination : 4 hours Full Marks : 100 (80 lectures; 1 unit; 4 credits) 1. NMR Spectroscopy (25 lectures): 1H, 13C, 31P, 19F NMR spectroscopy: preamble, principles of NMR, situation for other nuclei, continuous wave and pulsed NMR experiments, FID & processing FID, relaxation, chemical shifts and factors influencing it, origin of coupling, long-range coupling, coupling constant, Signal-to-Noise ratio (SNR), integration of signals, NOE, DEPT, APT; 2D NMR: basic of 2D NMR, general experimental scheme for 2D NMR, COSY, SECSY etc.; Extensive application of NMR to organic molecules. 2. UV- VIS (15 lectures): Definition of some simple terms: hyperchromic and hypochromic effect, bathochromic and hypsochromic effect, chromophore; conjugation and wavelength shifting; solvent effect on UV-Visible spectroscopy; Woodward, Woodward-Fieser and Nielsen’s rules for the determination of max to different organic molecules; structural study of simple and complex organic compounds and application to macromolecules, qualitative and quantitative uses. 3. IR and RAMAN (20 lectures): IR: Mode of vibration, overtone, combination and difference bands in IR spectroscopy; influencing factors of force constant, approach towards the analysis of an IR spectra; structural study of simple and complex organic compounds and application to macromolecules, qualitative and quantitative uses. Raman: Raman techniques, stokes and anti-stokes lines, utility to organic molecules. 4. MS: (20 lectures): MS: Base peak, molecular ion peak, metastable peak and their utility, fragmentation patterns to various organic molecules, description of LIMA, SIMS and FAB techniques in Mass spectroscopy; structural study of simple and complex organic compounds and application to macromolecules. GC-MS, LC-MS: principle and instrumentation of GC and LC; combined techniques (GC-MS, LC-MS) for chemical analyses. Recommended Books: 1. P.S. Sindhu 2. J.D. Graybeal 3. R.K. Harris 4. D.L. Pavia, G.M. Lampman and G.S.C. Kriz 5. Y.R. Sharma 6. H.Gunther : : : : Molecular Spectroscopy Molecular Spectroscopy Nuclear Magnetic Resonance Spectroscopy Introduction to Spectroscopy : Elementary Organic Spectroscopy : NMR Spectroscopy 10 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. J.K.M. Sanders and B.K. Hunter R.J. Abraham and P. Loftus E.A.V. Ebsworth, D.W.H. Roukin & S. Croadock I.D. Campbell and R.A. Dwek Williams & Fleming V.R. Dani P.S. Kalsi Silverstein, Bassler & Morrill Horst Friebolin H.C. Hill : Modern NMR Spectroscopy : Proton and Carbon-13 NMR Spectroscopy : Structural Methods in Inorganic Chemistry : Biological Spectroscopy. : Spectroscopic Methods in Organic Chemistry : Organic Spectroscopy : Spectroscopy of Organic Compounds : Spectrometric Identification of Organic Compounds : Basic one & two Dimensional NMR Spectroscopy : Mass Spectroscopy Course: Chem 524F Macromolecular Chemistry Examination : 4 hours Full Marks : 100 (80 lectures, 1 unit, 4 credits) 1. General idea on polymer (10 lectures): Introduction: polymer, monomer, oligomer, repeating units, structure of polymer molecules based on configuration and conformation, classification of polymers, intermolecular forces, biological and industrial importance of polymers, end group analysis, polymer solutions: thermodynamics of polymer dissolution, size and shape of macromolecules in solution. 2. Types and mechanism of polymerization (20 lectures): Types of polymerization reaction: chain polymerizations (free radical, ionic and coordination), step polymerizations (poly-condensation, poly-addition and ring-opening), mechanism of each polymerization, kinetics, chain length and degree of polymerization, initiation and initiation efficiency in free radical polymerization, gel effect, inhibition and retardation, elementary idea on oxidative and atom transfer radical polymerizations. 3. Copolymer (10 lectures) : Classification of copolymers, structure of copolymers, preparation of block and graft copolymers, kinetics of free radical copolymerization, reactivity ratio and its measurement, significance of reactivity ratio, copolymer equation for ideal and alternating copolymer. 4. Polymer Colloids (15 lectures): Latex, chemistry of polymer colloid formation: brief introduction on emulsion and dispersion polymerizations, general idea on solution, bulk and suspension polymerizations. Colloidal stability, applications of polymer colloids in paper, adhesives, coating and other industries. 5. Polymer degradation (15 lectures): Introduction, types of degradation: thermal degradation, factors affecting thermal degradation, mechanical degradation, degradation by ultrasonic wave, photodegradation, oxidative degradation, degradation by high energy and bactaria, hydrolytic degradation. 6. Monomers and related petrochemicals (10 lectures): Petrochemicals, classification of petrochemicals, distillation products from petroleum, reactions of alkanes, alkenes and aromatics, solvents and specific applications, synthesis of butadienes, acrylonitrile, acrylic acid, styrene, glycerine, surfactants etc. Recommended Books: 1. Royal Dutch (shell company) 2. Nelson 3. R.N. Shreve 4. B. K. Sharma 5. V.R. Gowariker et.al. 6. George Odian 7. Fred W. Bill Maeyer 8. Robert M. Fitch : : : : : : : : The Petroleum Handbook Petroleum Refining Engineering Chemical Process Industries Industrial Chemistry Polymer Science Principles of Polymerization A Textbook of Polymer Science Polymer Colloids: A Comprehensive Introduction Course: Chem 525F Stereochemistry and Conformations Examination : 4 hours Full Marks : 100 (80 lectures, 1 unit, 4 credits) 1. Conformations of heterocyclic rings (15 lectures): Six-membered ring with one heteroatom; conformation of cholesterols, cholestenone etc. 2. Stereochemistry of macromolecules (10 lecturer): Stereochemistry and stereo chemical control of polymerization by Zieglar Natta catalysts especially in polymerization of propylene, butadiene, isoprene etc. 3. Asymmetric synthesis using chiral reagents and achiral substrates (15 lectures): Hydrogen transfer from chiral reducing agents; use of asymmetric MPV reduction to determine the configuration of biphenyl derivatives; use of asymmetric Grignard reagents in creating chiral centers with stereoselectively. 4. The chemistry of organo transition-metal compounds (20 lectures): -Organotitanium compounds, the Tebbe reagent,. Acyl-iron complexes in enantioselective synthesis and in ketone synthesis, alkyne-cobalt complex, Pauson-Khand reaction in the synthesis of enones, telomerization from conjugated dienes; chromium (Cr)-arene complexes and its synthetic importance. 5. Stereochemistry of steroids (12 lectures): Configuration of nucleus and substituent groups; conformational analysis of steroids. 6. Stereochemistry of bi-cyclic systems (8 lectures): 5-3, 5-4, 5-5 (vit. biotin) and 6-6 (decalin) combinations. Recommended Books: 11 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Adams et.al. (ed.) H.O. House Carruthers H. Gilman L.F. Fieser and M. Fieser L.L. Finar R.KJ. Mackil and D.M. Smith P. Simpson T.W. Green R.O.C. Norman & J.M. Coxon : : : : : : : : : : Organic Reactions (all volumes) Synthetic Application of Organic Reactions Some Modern Methods of Organic Synthesis Advanced Organic Chemistry, (Vol-1 to IV) Topics in Organic Chemistry Organic Chemistry Vol. 2 A Guidebook to Organic Synthesis Organometallic Chemistry of the Main Group Elements Protective Groups in Organic Synthesis Principles of Organic Synthesis. Course: Chem 526F Advanced Organic Reactions Examination: 4 hours Full Marks : 100 (80 lectures, 1 unit, 4 credits) 1. Reaction mechanisms and methods of determining them (15 lectures): Types of mechanisms, type and reactions, kinetic and thermodynamic requirements for reactions, Hammond postulate, microscopic labeling, stereochemical, kinetic evidence, isotopic effects, the effects of molecular structure and environment on reaction rates in terms of reaction and transition states, topic includes theories of reaction rates, reactive intermediates, methods of elucidating reaction pathways, linear free energy relationships and solvent, acid-base, salt and kinetic hydrogen isotope effects. Application to selected reaction pathways. 2. Effects of structure on reactivity (13 lectures): Resonance and field effects, steric effects, quantitative treatments of the effect of structure reactivity, Hammett equations, Taft equation. 3. Aliphatic and aromatic nucleophilic substitutions (15 lectures): Neighboring group participation, non-classical carbocation, nucleophilic substitution at allylic carbon, aliphatic trigonal carbon, vinylic carbon, reaction medium phase transfer catalysis, aimbident nucleophile, regioselectivity, ambident substrates, reactive oxygen, sulfur, nitrogen and carbon nucleophiles. 4. Electrochemistry (10 lectures) : Principles of electrochemistry, cell parameters; electrochemical reaction: electroreduction of haloalkanes, aldehydes, ketones, nitrocompounds, conjugated compounds, Electrooxidation: Electrooxidation of carboxylic acid salt, and some aromatic compounds. 5. Rearrangements (12 lectures): Mechanisms, nucleophilic rearrangement, actual nature of migration, migratory aptitudes, memory effects, longer nucleophilic rearrangements, free radical rearrangement, dienone-phenol rearrangement, Favoriski, Fritsch-Buttenberg-Wiechell Sticglitz, Bayer-Villiger, Stevens rearrangement. Recommended Books: 1. Adams et.al. (ed.) 2. H.O. House 3. Carruthers 4. H. Gilman 5. L.F. Fieser and M. Fieser 6. P. Simpson 7. T.W. Green 8. Jerry March : : : : : : : : Organic Reactions (all volumes) Synthetic Application of Organic Reactions Some Modern Methods of Organic Synthesis Advanced Organic Chemistry, (Vol-1 to IV) Topics in Organic Chemistry Organometallic Chemistry of the Main Group Elements Protective Groups in Organic Synthesis Advanced Organic Chemistry Course: Chem 527F Bioorganic and Food Chemistry Examination : 4 hours Full Marks : 100 (80 lectures, 1 unit, 4 credits) 1. Enzyme-catalyzed reactions (15 lectures): Definition of enzyme, coenzyme and apoenzyme enzyme properties, enzyme inhibitors, origin of enzyme specificity, enzyme-catalyzed interconversion of acetaldehyde and ethanol, ester and carboxylic acid. Enzyme catalyzed SN2 reaction in living system, transamination reaction to an imine. Enzyme catalyzed Aldol & Claisen condensation reaction, Acyl transfer reaction in living system. 2. Molecular Recognition (15 lectures): Nucleic acid and some biological catalysts; introduction, recognition of guests by synthetic hosts, natural hosts, ionophores; molecular recognition by an enzyme, catalytically active antibodies, nucleic acids, cryptands, spherands, epitope and antigen. 3. Biomolecules (15 lectures): Occurrence, structure, stereochemistry and biological properties of lipids, prostaglandins and nucleic acids; biosynthesis of prostaglandins (e.g., PGI), nucleosides (e.g., adenosine, thymidine etc.), nucleotides and nucleic acids (e.g., RNA, DNA). 4. Food, food additives and preservation (10 lectures): Different classes of foods; types of food additives (polysorbate 60, dimethyl pyrocarbonate ), direct and indirect effect of food additives on health; chemical changes in food during storage at room temperature and at frozen state. 5. Food adulteration (10 lectures): Definition of adulterated food, common adulterants in different foods; contamination of foods with toxic chemicals, pesticides and insecticides; bacterial and fungal contamination of food. 6. Nutritional aspects of foods (15 lectures): Function of fats, phospholipids and cholesterol, essential fatty acid deficiency in human beings, effect of excess essential fatty acids, fatty liver and lipotropism, dietary lipids and their relation to the causation of atherosclerosis and ischaemic heart disease; protein efficiency ratio (PER), digestibility coefficient, biological values of protein, net protein utilization (NPU), net protein ratio (NPR), effect of amino acid imbalance and amino acid toxicity. 12 Recommended Books: 1. Seyhan Ege : 2. R.K. Bakiaski : 3. Harper : 4. M. Swaminathan : Organic Chemistry Structure & Reactivity. Modern Biochemistry Biochemistry Advanced Text book on Food and Nutrition, vol. I & II Course: Chem 521L Organic Chemistry Practical Examination : 24 hours Marks: 200 (2 unit, 8 credits) (i) Experiment: 140 marks (ii) Continuous Class Evaluation and class records: 60 marks 1. Crystallization, extraction, distillation and drying of organic compounds / reagents. 2. Fractional distillation: ethanol from sugar; extraction from solution. 3. Multistep organic synthesis: a) synthesis of nitrophenols, paracetamol; b) preparation of sulphanilamide and other sulphur drugs; c) synthesis of benzyllic acid from benzoin via benzil formation; d) preparation of acridone from anthranilic acids; e) methyl orange and salicylic acid from aspirin (some other synthesis may also be included if facilities are made available). 4. Preparation of ketals, esters: fats and detergents; reactions of aldehydes and ketones and heterocyclic compounds like coumarins, beta keto esters, cyclohexene from cyclohexanol 5. Chromatographic method - TLC, column chromatography, paper chromatography. 6. Assay of drugs and raw materials: a) ephedrine hydrochloride; c) penicillin/ ampicilline capsule; d) cotrimoxazole tablet /syrup; e) aspirin tablet etc. (some other suitable compounds if they are available. Use of UV-Vis and IR spectrometers. 7. Resolution of recemic compounds (acids/bases). 8. Oxidation: selective oxidation; oxidation of primary and secondary alcohol and aldehyde. 9. Reduction: sodium borohydride reduction of benzil and other compounds containing carbonyl groups. 10. Hydroboration: hydroboration of unsaturated hydrocarbons. 11. Phase Transfer Catalysis: Use of PTC in different types of reactions. 12. Reaction kinetics: hydrolysis of tert-butyl chloride etc. Course: Chem 599 Organic/Industrial Chemistry Thesis Marks: 200 (2 unit, 8 credits) (i) (ii) Thesis submission: 140 marks Thesis defense: 60 marks 13 INORGANIC CHEMISTRY BRANCH: Courses Course Titles Unit Credit Marks Chem 531F Organometallic Chemistry 1.0 4 100 Chem 532F Bio-inorganic Chemistry 1.0 4 100 Chem 533F Inorganic Materials 1.0 4 100 Chem 534F Analytical Chemistry 1.0 4 100 Chem 535H Homogeneous & Heterogeneous Catalysis 0.5 2 50 Chem 536H Environmental Chemistry 0.5 2 50 Chem 531AH Class Assessment 0.5 2 50 Chem 531VH Viva-voce 0.5 2 50 Chem 531L* Inorganic Chemistry Practical & Project 2 8 200 8.0 32 800 OR Chem 599** Thesis / Dissertation on topics of Inorganic Chemistry Total Credit Courses available * Laboratory courses include 30% (60) marks for continuous Lab. assessment. ** Thesis includes 30% (60) marks for oral examination on the thesis. Examination of the theory courses of 100 marks (1.0 unit, 4 credits) shall be of 4 (four) hours duration, of 50 marks (0.5 unit, 2 credits) of 2 (two) hours duration and of the practical courses of 100 marks (1.0 unit, 4 credits) shall be of 12 (twelve) hours duration (2 days). 30% marks of the practical courses are assigned for continuous Lab. assessment. The students shall submit a report after each lab. class to the lab. teacher(s) for evaluation. After evaluation the report shall be returned to the students. The lab. teacher(s) shall submit the average marks of all lab. evaluation in sealed envelopes to the chairman of the relevant examination committee within three weeks from the last Lab. held. Class assessment course includes tutorial, terminal, home assignment, and /or class examinations taken on theoretical courses by the relevant course teacher(s) during the academic year. Class assessment comprises (a) 80% marks in tutorial, terminal, home assignment and /or class examinations and (b) 20% marks for attendance in the class. The class teacher(s) of each course shall submit the average consolidated marks of class assessments and attendance in sealed envelope to the Chairman of the relevant examination committee within three weeks from the last class held. Viva-voce examination includes the assessment of the students through oral examination of all the courses. No student having less than 60% class attendance shall be allowed to sit for the examination. Course : Chem 531F Organometallic Chemistry Examination : 4 hours Full Marks : 100, (1 unit, 4 credits) (80 lectures, 4 lectures per week) 1. 2. Application of different spectroscopic techniques to resolve structural problems of ligands and their complexes (10 Lectures). Organotransition-metal complexes of classic Lewis-base donors, phosphines and other group-VB donors and hydrides (10 Lectures). 3. Unsaturated nitrogen ligands (11 lectures): macrocyclic imines, dinitrogen complexes, nitrous oxide, nitroso arenes, nitric oxide complexes, diazonium complexes, diazoalkane complexes, nitrite complexes, imines and nitrides. 4. Types of organometallic reactions (30 lectures) : a) Oxidative-additions: reaction with protons, reactions forming metal-carbon bonds, reaction with hydrogen. b) Reductive-eliminations: reaction forming carbon-carbon bonds, reactions forming carbon-hydrogen bonds. c) Insertion reactions: migratory insertions, acyl formation, stereochemistry at the metal and alkyl carbon. d) Intermolecular nucleophilic additions to unsaturated ligands: attack on coordinated CO, acyl, olefin, acytylene, arene, 3-allyl and 5-C5H5. 5. Chemistry of the iron group metallocenes (19 lectures): Ferrocene: preparation, electronic structure and bonding, physical properties, reactions, general aspects, comparative reactivities of ferrocene and bonzonoid aromatics, mechanism of electrophilic substitution, mechanism of the arylation reaction. Recommended Books: 1. Parcell and Kotz : Inorganic Chemistry 2. Cotton and Wilkinson : Advanced Inorganic Chemistry, 5th Edn. (1980) 3. J.P. Collman and : Principles and Applications of L.S. Hegedus Organo-transition Metal Chemistry 4. J.E. Huheey : Inorganic Chemistry: Principles of Structure and Reactivity 5. J.D. Atwood : Inorganic and Organometallic Reaction Mechanism. 6. W.U. Malik G.D. Tuli & : Selected Topics in Inorganic R.D. Madan Chemistry 7. S.Z. Haider : Selected Topics in Inorganic Chemistry 8. D.L. Pavia, G.M. Lavepman & : Introduction to Spectroscopy G.S. Kriz (Saunders) 14 Course : Chem 532F Bioinorganic Chemistry Examination : 4 hours Full Marks : 100, (1 unit, 4 credits) (80 lectures, 4 lectures per week) 1. Background: (7 Lectures) : a) Essential amino acids, peptides, proteins, enzymes and metalloenzymes. b) Biological classification of essential elements, trace elements and its classification, role of essential trace elements in human nutrition. 2. Biochemistry of Iron (30 lectures) : (a) Iron storage by Ferritin and transport by transferrin; Siderophores and bacterial iron transport. (b) Heme Proteins e.g., Hemoglobin and myoglobin; nature of the heme- dioxygen (O2) binding and the model system, cooperative O2 binding in Hemoglobin, Hemerythrins. (c) Classifications and functions of Cytochromes, Cytochrome P450 enzymes. (d) Iron-sulphur proteins, High-potential iron-sulphur proteins (HiPIPs), Ferredoxins, Rubredoxins. 3. Biochemistry of other metals (30 lectures) : a) Zinc (Zn) : Structures of Carboxypeptidases and Carbonic anhydrase, and the mechanistic model of their functions. b) Copper (Cu) : Functions of various Cu proteins e.g., Hemocyanins, Ceruloplasmin, Cu transport by seram Albumin, Role of Catalases, peroxidases and Super oxide dismutase. c) Cobalt (Co) : Structure, Functions and Coenzymes of vitamin B12 . d) Metallothioneins. 4. Hydrogenases and their physiological significance; Biological Nitrogen fixation (7 lectures): hypothesis for molybdenum nitrogenase; Concept of other nitrogenase e.g., all-iron nitrogenase, Vanadium nitrogenase. 5. Metal pollution metal toxicity in human health, Carcinogens and Mutagens. Treatment of Cancer, Rheumatoid Arthritis and Mental disorder by drugs and medicines containing various metals. (6 lectures). Recommended Books: 1. Cotton and Wilkinson 2. Counther L. Eichhorn 3. J.E. Huheey 4. A.C. Deb 5. K.F. Purcell & J.C. Kotz 6. M.N. Hughes 7. R.J.P. Williams & De Silva 8. E. Ochiai 9. David R. Williams, (Edited) 10. R.W. Hay 11. D.M. Taylor, D:R. Williams 12. Bertini, I & Gray, H.B. Lippard,, S.J., Valentine, J.S., : : : : : : : : : : : : Advanced Inorganic Chemistry, 5th Edn. (1980) Inorganic Biochemistry, (edited) Vol. I & II Inorganic Chemistry: Principles of Structure and Reactivity. Fundamentals of Biochemistry Inorganic Chemistry The Inorganic Chemistry of Biological Processes New Trends in Bioinorganic Chemistry Bioinorganic Chemistry: An Introduction to Bioinorganic Chemistry Bioinorganic Chemistry Trace Element, Medicine and Chelation Therapy. Bioinorganic Chemistry Course : Chem 533F Inorganic Materials Examination : 4 hours Full Marks : 100, (1 unit, 4 credits) (80 lectures, 4 lectures per week) 1. Introduction to materials science and engineering (9 lectures) : Materials and civilization, types of materials, materials and engineering, structure, properties, performance. 2. Atomic bonding and coordination (11 lectures) : Individual atoms and ions, molecules, macromolecules (polymers), threedimensional bonding and interatomic distances. 3. Crystals (Atomic Order) (13 lectures) : Crystalline phases, cubic structures, noncubic structures, polymorphism, unit-cell geometry, crystal directions, crystal planes . 4. Characterisation of Solid Materials (13 lectures) : b) X-ray diffraction: Structure determination from powder patterns, influence of crystal symmetry and multiplicities on powder pattern, limitation of powder methods, single crystal X-ray method. c) Neutron diffraction: Neutron diffraction, applications, merits and limitation. d) Electron Microscopy: Electron diffraction applications, transmission electron microscopy. e) 5. Scanning electron microscopy (SEM), analytical electron microscopy. The physical properties of materials (11 lectures) : Density, thermal properties, diffusion, electrical properties, magnetic properties, dielectric and optical properties. 15 6. Performance of materials in service (12 lectures) : Service performance, corrosion reactions, corrosion control, delayed fracture, performance of metals at high temperatures, service performance of polymers, performance of ceramics at high temperatures. 7. Superconductors (13 lectures) : Superconductivity, Theories of superconductivity, introduction of low T c and high Tc superconducting materials, applications, recent development of superconducting materials. 8. Liquid crystals (13 lectures): Classification of liquid crystals and their possible phase transitions, chemical structure elements in liquid crystals, application of liquid crystals. Reference : 1. Lawrence H. Van Vlack 2. R.E. Smallman and R.J. Bishop 3. O.P. Khanna 4. A.R. West 5. A.K. Cheetham and P. Dey 6. A.R. West 7. W. D. Callister. Jr. 8. C.E. Hall 9. P.J. CÒllings and M. Hird : : : : : : : : : Elements of Materials Science and Engineering Metals and Materials Material Science and Metallurgy Solid State Chemistry and its Applications Solid State Chemistry Techniques Basic Solid State Chemistry Materials Science and Engineering- An Introduction Introduction to Electron Microscopy Introduction to liquid crystals: Chemistry and Physics Course : Chem 534F Analytical Chemistry Examination : 4 hours Full Marks : 100, (1 unit, 4 credits) (80 lectures, 4 lectures per week) 1. Sampling (7 lectures) : Water , air and soil, sample processing, trace analysis. 2. Atomic spectroscopy (12 lectures): Absorption, emission and fluorescence methods: theory, measurement, interference and applications. 3. Electron spectroscopy (8 lectures) : ESCA, AES (AUGER). 4. X-ray spectroscopy (11 lectures) : Absorption, diffraction and fluorescence 5. Potentiometric methods (13 lectures): Indicator electrodes, membrane indicator electrodes; glass electrode for pH measurements, liquid membrane electrodes, solid state and precipitate electrodes, pH meters, errors affecting pH measurements with glass electrodes, direct potentiometric measurements, calibration for direct potentiometry, standard addition method, potentiometric titrations, end point determination 6. Electrogravimetry and coulometry (10 lectures): Theory, instruments and applications. 7. Voltammetry and polarography (13 lectures): Theory of hydrodynamic voltammetry and classical polarography; measurement and applications; anodic stripping voltammetry. 8. Thermal analysis (6 lectures): Differential thermal analysis and differential scanning calorimetry, thermogravimetry and thermometric titrations Recommended Books: 1. D.A. Skoog : Principles of Instrumental Analysis (4th Ed.) 2. Willard, Merritt, Dean & Settle : Instrumental Methods of Analysis (6th Ed.) 3. Bassett, Danney, Jeffery & Mendhams : Vogel's Textbook of Quantitative Inorganic Analysis 4. Pavia, Lampman & Kriz : Introduction to Spectroscopy 5. L.R. Faulkner & A.J. Bard : Electrochemical Methods Course : Chem 535H Homogeneous and Heterogeneous Catalysis Examination : 2 hours Full Marks : 50, (0.5 unit, 2 credits) (40 lectures, 2 lectures per week) 1. Introduction (2 lectures): Definition and thermodynamics of catalysis, comparisons between homogeneous and heterogeneous catalysis, industrial application. 2. Inorganic reaction mechanism (12 lectures) : i) Review of rate laws, activation parameters, substitution reaction on squere planar and octahedral complexes, electron transfer reactions. ii) Stereochemical non-rigidity. 3. Homogeneous catalysis: (i) Overview of mechanism, monohydride catalysts, dihydride catalysts. (ii) General features of Wilkinson’s catalyst and mechanisms of hydrogenation by Rhodium (I) dihydride catalysts, asymmetric homogeneous hydrogenation, asymmetric catalysts of the type RhCIL 3 and other asymmetric homogeneous catalysts. 4. Hydrogenation of olefin and acetylene (10 lectures): Hydrogenation of conjugated olefins and acetylene, hydrogenation of other functional groups, catalytic hydrogenation of arenes, a model for hydrogenase and free radical hydrogenation. 5. Synthesis characterization and Stoichiometric reactions of transition-metal hydrides (5 lectures) . 16 6. Catalytic reaction involving carbon monoxide and hydrogen cyanide (11 lectures): (i) Oxo reactions; cobalt catalysts, rhodium catalysts and other oxo catalysts (ii) Fischer-Tropsch reaction; hydrogeneous Fischer-Tropsch catalysts, hydrogeneous model reactions and homogeneous CO hydrogenation. Recommended Books: 1. Parcell and Kotz 2. Cotton and Wilkinson 3. J.P. Collman and L.S. Hegedus 4. J.E. Huheey 5. J.D. Atwood 6. W.U. Malik G.D. Tuli & R.D. Madan 7. S.Z. Haider : : : : : : : Inorganic Chemistry Advanced Inorganic Chemistry, 5th Edn.(1980) Principles and Applications of Organo-transition Metal Chemistry Inorganic Chemistry: Principles of Structure and Reactivity Inorganic and Organometallic Reaction Mechanism. Selected Topics in Inorganic Chemistry Selected Topics in Inorganic Chemistry Course: Chem 536H Environmental Chemistry Examination : 2 Hours Full Marks : 50, (0.5 unit, 2 credits) (40 lectures, 2 lectures per week) 1. Introduction (5 lectures) : Environmental science and environmental chemistry, definitions of some environmental terms, spheres of the environment, the natural cycles of environment. 2. Hydrosphere (10 lectures): Carbon dioxide in water, pH of natural water, behaviour of metal ions in water, complexing agents and humic substances in natural water, microbially mediated redox reactions. 3. Lithosphere (10 lectures): Composition of lithosphere, water and air in soil, inorganic and organic components in soil, acidbase and ion-exchange reactions in soil, micro- and macro-nutrients. 4. Heavy metal pollution (9 lectures): Pollution sources, Biochemical and toxicological effects of lead, mercury, cadmium, arsenic, chromium, selenium and radon.. 5. Waste and hazardous substances: Introduction, sources and classification of hazardous substances and wastes, hazardous wastes in the geosphere, hydrosphere, atmosphere and biosphere. 6. Noise Pollution (6 Lectures) : Classification, measurements of noise, noise pollution hazards and its controls. Recommended Books: 1. S.E. Manahar 2. A.K. De 3. S.S. Dara 4. Colin Baird : : : : Environmental Chemistry (6th Edn.) Environmental Chemistry (5th Edn.) A Text Book of Environmental Chemistry and Pollution Control. Environmental Chemistry. Course : Chem 531L Inorganic Chemistry Practical & Project Examination : 24 hours Full Marks : 200 (2 unit, 8 credits) Experiment & Project- 140 Continuous Class Evaluation : 60 1. Preparation of 1-10 phenanthroline, ethylenediamine, orthophenyline diamine, picolinic acid, salicylic acid, oxalic acid, orthoamino benzoic acid complexes of Co(III), Cu(II), Ni(II), Cr(III), Fe(II), Fe(III); characterization by elemental, magnetic measurement & spectroscopic method. 2. Ion-exchange separation & estimation of some metal ions: Cu(II), Ni(II) Co(III) and some heavy metals. 3. Extraction & estimation of magnesium from green leaves 4. Estimation of arsenic in water. 5. Preparation of metal-acetylacetonate complexes and separation of metal complexes by chromatographic techniques. 6. Solvent extraction method: Separation & estimation of metal ions. 7. Preparation & characterization of thiocynate complexes of transition metals containing some monodentate & bidentate ligands. 8. Separation & estimation of metals from some inorganic drugs. 9. Synthesis and characterization of molybdenum oxide clusters. Recommended Books: 1. J. Bassett & others : Vogel's Textbook of Quantitative Inorganic Analysis 2. Skoog & West : Fundamentals of Analytical Chemistry 3. Schwarzenbach & Flaschka : Complexometric Titrations.