Course : Chem 401F

Course : Chem-512F

Spectroscopy-II

Examination - 4 Hours

Full Marks : 100 (1 unit, 4 credit)

(80 lectures, 4 lectures per week, total 20 weeks)

1. 
   Raman spectroscopy (20 lectures): Classical and quantum theory; rotational Raman spectrum; instrumentation; effect of nuclear spin; molecules without a centre of symmetry; vibrational Raman spectra; mutual exclusion principles; polarization of Raman lines. Group theoretical analysis of vibrational spectra; vibrational analysis of single crystals; determination of structure by the application of Raman and infrared selection rules; vibrational-rotational Raman spectra; hyper Raman effect.
   
2. 
   NMR spectroscopy (20 lectures): (a) ¹³C, ¹⁹F, ¹⁴N, ¹⁵N, ³¹P NMR spectroscopy. (b) Multiple pulse NMR experiments with some simple applications. (c) Some two-dimensional NMR experiments, CIDNP experiments.
   
3. 
   Fluorescence spectroscopy (10 lectures): transition probabilities and lifetime, quantum yield, fluorescence intensity and polarization, fluorophores and fluorescence probes, fluorescence parameters, molecular dynamics study.
   
4. 
   Electron spin (paramagnetic) resonance spectroscopy (ESR / EPR) (10 lectures): Introduction; principles; instrumentation; spectrum; hyperfine structure; radicals; anions of aromatic hydrocarbons; relation between hyperline-splitting and unpaired electron density; interpretation of ESR spectra; ESR spectra of transition metal complexes as single crystals; applications.
   
5. 
   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.
   
6. 
   Mossbauer spectroscopy (10 lectures): Principles; experimental methods; theoretical aspects; quadrupole splitting; magnetic hyperfine interaction; internal magnetic field in molecules; applications.
   

Books recommended:

1. 
   D.A. Skoog : Principles of Instrumental Analysis
   
2. 
   B.P. Straughan & S. Walker : Spectroscopy
   
3. 
   B.K. Sharma : Spectroscopy
   
4. 
   C.N. Banwell : Fundamentals of Molecular Spectroscopy
   
5. 
   P.S. Sindhu : Molecular Spectroscopy
   
6. 
   I.D. Campbell & R.A. Dwek : Biological Spectroscopy
   
7. 
   D. Freifelder : Physical Biochemistry
   

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Course: Chem-513F

Electrolyte solution and Electrode Processes

Examination - 4 Hours

Full Marks : 100 (1 unit, 4 credit)

(80 lectures, 4 lectures per week, total 20 weeks)

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 natuer 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.
   

Books Recommended:

1. 
   D. Eisenberg and w. Kauzmann : The Structure and Properties of Water
   
2. 
   J.O’M. Bockris and A.K.N. Reddy : Introduction to Electrochemistry
   
3. 
   B.E. Conway : Electrode Processes
   
4. 
   K.J. Vetter : Electrochemical Kinetics
   
5. 
   G. Khortum : Treatise on Electrochemistry
   
6. 
   L. Anthrpov : Theoretical Electrochemistry
   
7. 
   W. Blum and G.B. Hogaboom : Principles of Electroplating and
   

Electroforming

8. 
   Kohler and Creighton : Electrochemistry –
   

Principles and Applications

9. 
   Mars G. Fontans and Greene : Corrosion Engineering
   
10. 
    S.N. Banerjee : An Introduction to the Science of
    

Corrosion and Its Inhibition

11. 
    E. C. Potter : Electrochemistry –
    

Principles and Applications

12. 
    G. Mantell : Industrial Electrochemistry
    
13. 
    M.R. Rifi and Frank H. Covitz : Introduction to Organic
    

Electrochemistry

14. 
    Demetrios K. Kyriacou : Basics of Electro-organic Synthesis
    

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Course : Chem-514F

Advanced Chemical Kinetics

Examination - 4 Hours

Full Marks : 100 (1 unit, 4 credit)

(80 lectures, 4 lectures per week, total 20 weeks)

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 = H₂ + Br₂); thermodynamic formulation of CTST; assumptions and limitations of CTST; multiple crossing and the equilibrium hypothesis; reparability of the reaction co-ordinate; 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. 
   Elementary 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, rate-determining 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, para-ortho 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 (7th edition)
   
2. 
   Keith J. Laidler : Chemical Kinetics (3rd. edition)
   
3. 
   S. Glasstone, K.J. Laidler & H. Eyring : The Theory of Rate Processes
   
4. 
   K.J. Laidler and J.H. Meiser : Physical Chemistry
   

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Course : Chem-515F

Physical Chemistry of Macromolecules

Examination - 4 hours

Full marks : 100 (1 unit, 4 credit)

80 lectures, 4 lectures per week, total 20 weeks

1. 
   Introduction to macromolecules: (13 lectures): The macromolecular concept; some basic terms and definitions: monomer, oligomer and polymer; repeating unit; end groups; degree of polymerization. Polymer molecular weights and distributions and their determination: osmotic pressure measurements (M_n), Light scattering measurements (M_w), sedimentation velocity and sedimentation equilibrium methods (M_z), viscosity and molecular weight (Mv); natural and synthetic polymers; polymerization and functionality principle; linear, branched and cross-linked (network) polymers; thermoplastics and thermosets; elastomers, fibres and plastics; copolymers; polymer nomenclature; isomerism in polymers: positional, stereo and geometrical isomerism.
   
2. 
   Condensation or step-growth polymerization (10 lectures): Various types of condensation polymers: polyesters, polyamides, polyurethanes, polycarbonates, polyethers, and inorganic polymers. Kinetics of linear condensation polymerization; relation between average functionality, extent of reaction, and degree of polymerizatin: Carothers’ equation; bifunctional systems; molecular weight distribution in linear condensation polymerization; factors influencing maximum attainable molecular weight.
   
3. 
   Addition polymerization (15 lectures): Comparison between step-growth and addition polymerization processes; addition polymerization: free radical, cataionic and anionic; monomers and initiators; effect of substituents on the polymerization mechanism of vinyl polymers;n. Overall scheme of a free radical polymerization process: methods of radical production, efficiency of initiators, chain propagation, transfer and termination. Kinetics of free radical polymerization, kinetic chain length and average degree of polymerization; chain tansfer and incorporation of its effects in ideal polymerization model; chain transfer constants; inhibition and retardation; deviations from ideal kinetics.
   
4. 
   Chain growth copolymerization (10 lectures): Coplymerization models; copolymer composition equation from simple (terminal) copolymerization model; characteristics of monomer reactivity ratios; random copolymers, alernating copolymers, formation of long sequences of one monomer unit; azeotropic copolymerizatios; average composition of binary copolymers. Determination of reactivity ratios. Reactivities of monomers and radicals: resonance effects, polar effects and steric effects; the Q–e scheme, rates of free radical copolymerization.
   
5. 
   Biomacromolecules (10 lectures): Building-block molecules of bio-molecules and their nature; simple ideas of structure and functions of proteins / enzymes, lipids, carbohydrates, and DNA / RNA. Stabilizing forces in biological macromolecules; native and denatured forms of proteins.
   
6. 
   Specificity and modifications of proteins / enzymes (5 lectures): Trypsin; chymotrypsin; elastage; carboxypeptidase; aminopeptidase; cyanogen bromide cleavage; chemical modification of SH, -S-S-, NH₂, imidazole and –S-CH₃ groups of proteins.
   
7. 
   Isolation and purification methodology of proteins / enzymes (5 lectures): Chemistry of solubilization, precipitation and chromatographic separation of proteins.
   
8. 
   Characterization of proteins (12 lectures): Gel filtration (gel permeation chromatography, GPC); Electrophoresis; 2D peptide mapping; N and C-terminal analysis; aminoacid analysis and degradation of proteins. Enzyme nomenclature; cofactor; enzyme catalyzed reactions having one substrate; Michaelis-Menten approach to enzyme kinetics; K_m and V_m values and their determination; enzymatic assay.
   

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
   
6. 
   A. W. Lehninger : Principles of Biochemistry
   
7. 
   R.C. Bohinski : Modern Concepts of Biochemistry
   
8. 
   G. Zubay : Biochemistry
   
9. 
   D. Freifelder : Physical Biochemistry
   
10. 
    R.K. Scopes : Protein Purification
    
11. 
    C.N. Price & R.A. Dwek : Principles and Problems in Physical
    

Chemistry for Biochemists.