I Stereochemistry and Bonding in Main Group Compounds
VSEPR Theory, Walsh diagrams (tri- and penta- atomic molecules), dp-pp bonds. Bent rule and energetics of hybridization, some simple reactions of covalently bonded molecules.
II Metal-Ligand Equilibria in Solution
Stepwise and overall formation constants and their interaction, trends in stepwise constants, factors affecting the stability of metal complexes with reference to the nature of metal ion and ligand, chelate effect and its thermodynamic origin, determination of binary formation constants by pH-metry and spectrophotometry.
III Metal - Ligand Bonding
Limitation of Crystal field theory, molecular orbital theory, octahedral, tetrahedral and square planer complexes, p bonding and molecular orbital theory. (MOT).
IV Isopoly and Heteroply Acids and Salts.
V Metal p-Complexes
Metal carbonyls, metal nitrosyls, structure and bonding, Vibrational spectra of metal carbonyls for bonding and structural elucidation & important reactions of metal carbonyls; preparation, bonding structure and important reactions of transition metal nitrosyl; dinitrogen and di oxygen complexes; tertiary phosphine as ligand, metal olefin complexes – structure and bonding.
M.Sc., Chemistry; Semester-I
CHE-C 122 : Organic Chemistry
60 Hours (4 hr/per week)
I.Nature of Bonding in Organic Molecules
Delocalized chemical bonding, conjugation, resonance, hyper-conjugation, bonding in fullerenes, tautomerism. Aromaticity in benzenoid and non benzenoid compounds, alternant and non-alternant hydrocarbons, Huckel's rule, energy level of p-molecular orbitals, annulenes, anti-aromaticity, y-aromaticity, homo-aromaticity, PMO approach, Bonds weaker than covelent- addition compounds, crown ether complexes and cryptands, inclusion compounds, cyclodextrins.
II.Reaction Mechanism; Structure and Reactivity:
Types of mechanism, types of reactions. Thermodynamic and kinetic requirements, kinetic and thermodynamic control. Hammond's postulate. Curtin-Hammett principle. Potential energy diagrams, transition states and intermediates, methods of determining mechanisms, isotope effects. Hard and soft acids and bases.
Generation, structure, stability and reactivity of carbocations, carbanions, free radicals, carbenes and nitrenes.
Effect of structure on reactivity - resonance and field effects, steric effect, quantitative treatment. The Hammett equation and linear free energy relationship. Substituent and reaction constants. Taft equation.
III.Aliphatic Nucleophilic Substitution:
The SN2, SN1, mixed SN1 and SN2 and SET mechanisms.
The neighbouring group-mechanism: neighbouring group participations by p and s bonds, anchimeric assistance, Classical and nonclassical carbocations, norbornyl system, common carbocation rearrangements.
The SNi mechanism:
Nucleophilic substitution at an allylic, aliphatic trigonal and a vinylic carbon. Reactivity: The effects of substrate structure, Attacking nucleophile, Leaving group and Reaction medium; Phase transfer catalysis.
IV.Addition to Carbon-Hetero Multiple Bonds
Mechanism of metal hydride reduction of saturated and unsaturated carbonyl compounds, acids esters and nitriles. Addition of Grignard reagents, organo- zinc and organo-lithium reagents to carbonyl and unsaturated carbonyl compounds. Wittig reaction. Mechanism of condensation reactions involving enolates- Aldol, Knoevenagel, Claisen, Mannich, Benzoin, Perkin and Stobbe reactions.
V. Free Radical Reactions
Types of free radical reactions and their detection. Free radical substitution mechanism, mechanism at aromatic substrates. Reactivity in the attacking radicals. The effect of solvents on reactivity.
Allylic halogenations (NBS) oxidation of aldehydes to carboxylic acids, auto-oxidation, Radical coupling, arylation of aromatic compounds by diazonium salts. Sand Meyer reaction. Free radical rearrangement. Hunsdiecker reaction.
M.Sc. Chemistry Semester I
CHE-C 123 : Physical Chemistry
60 Hours (4 Hr/per Week)
I Quantum Chemistry
A Introduction to Exact Quantum Mechanical Results
The Schrodinger equation and the postulates of quantum mechanics. Discussion of solutions of the Schrodinger equation to some model systems viz., particle in a box, the harmonic oscillator, the rigid rotor, the hydrogen atom.
B Approximate Methods
The variation theorem, linear variation principle. Perturbation theory (first order and non-degenerate). Applications of variation method and perturbation theory to the Helium atom
C Molecular Orbital Theory
Huckel theory of conjugated systems, bond order and charge density calculations. Applications to ethylene, butadiene, cyclopropenyl radical, cyclobutadiene etc. Introduction to extended Huckel theory.
A. Classical Thermodynamics
Brief resume of concepts of laws of thermodynamics, free energy, chemical potential and entropies. Partial molar properties; partial molar free energy, partial molar volume and partial molar heat content and their significance. Determination of these quantities. Concept of fugacity and determination of fugacity
Non-ideal systems: Excess functions for non ideal solutions. Activity and activity coefficient, Debye-Huckel theory for activity coefficient of electrolytic solutions; determination of activity and activity coefficients; ionic strength.
III. Chemical Dynamics
Methods of determining rate laws, collision theory of reaction rates, steric factor, activated complex theory, Arrhenius equation and the activated complex theory; ionic reactions, kinetic salt effects, steady state kinetics, kinetic and thermodynamic control of reactions, treatment of unimolecular reactions.
IV. Surface Chemistry
Surface tension, capillary action, pressure difference across curved surface (Laplace euqation), vapour pressure of droplets ( Kelvin equation), Gibbs adsorption isotherm, estimation of surface area (BET equation) surface films on liquids (Electro-kinetic phenomenon), catalytic activity at surfaces.
Surface active agents, classification of surface active agents, micellization, hydrophobic interaction, critical micellar concentration (CMC), factors affecting the CMC of surfactants, counter ion binding to micelles, thermodynamics of micellization-phase separation and mass action models, solubilization, micro emulsion, reverse micelles.
Electrochemistry of solution. Debye-Huckel. Onsagar treatment and its extension, ion solvent interactions. Dye-Huckel- Jerum mode. Thermodynamics of electrified interface equations. Derivation of electro-capillarity. Lippmann equations (surface excess), methods of determination. Structure of electrified interfaces. Guoy-Chapman, Stern, Graham Devanathan- Mottwatts. Tobin, Bockris, Devanathan models.
Over potentials, exchange current density, derivation of butler-Volmer equation, Tafel plot.
Quantum aspects of charge transfer at electrodes-solution interfaces, quantization charge transfer, tunneling .
M.Sc. Chemistry Semester I
CHE-C 124 : Group Theory and Spectroscopy
45 Hours (3 Hrs/ week)
I.Symmetry and Group Theory
Symmetry elements and Symmetry operations, definitions of group, subgroups, relationship between orders of finite group and its subgroup. Schonflies symbols, representations of groups by matrices (representation for the Cn, Cnv, Cnh, etc groups to be worked out explicitly). Character of a representation. The great orthogonality theorem (without proof) and its importance. Character tables and their use in spectroscopy.
II.Unifying principles :
III.Electromagnetic radiation, interaction of electromagnetic radiation with matter – absorption, emission, transmission, reflection, refraction, dispersion, polarization and scattering. Uncertainty relation and natural line width and natural line broadening, transition probability, results of time dependent perturbation theory, transition moment, selection rules, Intensity of spectral lines, Born Oppenheimer approximation, rotational, vibrational and electronic levels.
Classification of molecules, rigid rotor model, effect of isotopic substitution on the transition frequencies, intensities , non rigid rotors. Stark effect and effect of external field. Applications.
IV. Vibrational spectroscopy
A. Infrared Spectroscopy:
Review of linear harmonic oscillator, vibrational energies of di atomic molecules, Zero point energy force constants, anharmonicity, Morse potential energy diagrams, vibration-rotation spectroscopy, PQR branches, breakdown of Oppenhimer approximation, vibration of poly atomic molecules, selection rules, normal modes of vibrations, group frequencies, overtones, hot bands, factors affecting band positions and intensities, far IR region, metal ligand vibrations, normal coordinate analysis.
B. Raman Spectroscopy: Classical and quantum theories of Raman effect. Pure vibrational- rotational Raman Spectra, mutual exclusion principle, Resonance Raman Spectroscopy, coherent anti-stokes Raman Spectroscopy (CARS).
Energies of atomic orbitals, vector representation of momenta and vector coupling, spectra of hydrogen atoms and alkali metal atoms.
B. Photo electron spectroscopy
Basic principles, photo-electric effect, ionization process, Koopman’s theorem, photo electron spectra of simple molecules, ESCA, chemical information from ESCA. Auger electron spectroscopy – basic idea.
M.Sc. Chemistry Semester I
CHE-C 125A : Mathematics for Chemists
30 Hours (2 Hr/per Week)
1. Vectors in Matrix algebra
Vectors , dot, cross and triple products etc.. The gradient, divergence and curl. Vector calculus, Gauss’ theorem, divergence theorem etc.,
Addition and multiplication,; inverse, adjoint and transpose of matrices, special metrics (symmetric, skew –symmetric, Hermitian, skew- Hermitian, unit diagonal , unitary etc ) and their properties. Matrix equations: Homogenous, non-homogenous linear equations and conditions for the solution, linear dependence and independence.
Introduction to vectors spaces, vectors eigenvalues and eigenvectors, diagonalization, determinants (examples from Huckel theory).
Introduction to tensors, polarizability and magnetic susceptibility as examples.
Functions, continuity and differentiability, rules for differentiation, application of differential calculus including maxima and minima (examples related to maximally populated rotational energy levels, Bohr’s radius and most probable velocity from Maxwell’s distribution etc), exact and inexact differentials with their applications to thermodynamic properties.
Integral calculus, basic rules for integration, integration by parts, partial fraction and substitution, Reduction formulae, applications of integral calculus.
Functions of various variables, partial differentiation, coordinate transformations (for example Cartesian to spherical polar), curve sketching.
III. Elementary Differentla equations
Variables – separable and exact first order differential equations, homogenous, exact and linear equations. Applications to chemical kenetics, secular equilibria, quantum chemistry etc. Solutions of differential equations by power series method, Fourier series, solution of harmonic oscillator and Legendre equation etc., speherical harmonics, second order differential equations and their solutions.
IV Permutation and Probability
Permutations and combinations, probability and probability curves, average, root mean square and most probable errors, examples from the kinetic theory of gases etc, curve fitting (including least square fit etc.) with a general polynomial fit.
M.Sc. Chemistry Semester I
CHE-C 125B : Biology for Chemists
30 Hours (2 Hr/per Week)
I. Cell Structures and Functions
Structure of prokaryotic and eukaryotic cells, inter cellular organelles and their functions, comparison of plant and animal cells. Overview of metabolic processes – catabolism and anabolism. ATP – a biological energy currency. Origin of life – unique properties of carbon, chemical evolution and rise of living systems, Introduction to bio-molecules, building block of bio-macro molecules.
Conformation of mono saccharides, structure and functions of important derivatives of mono- saccharides viz., glycosides, deoxy sugars, myoinositol, amino sugars. N – acetyl muramic acid, sialic acid, di- saccharides and ploy saccharides,. Sturctural poly saccharides, cellulose and chitin.storage poly saccharides – starch and glycogen.
Structural and biological functions of glucosaminoglycans or mucoploy saccharides. Carbohydrates of glycoproteins and glycol lipids. Role of sugars in biological recognition. Blood group substances. Ascorbic acid.
Fatty acids, essential fatty acids, structure and function of triglycerols, glycerol phospholipids. Sphingolipids, cholesterol, bile acids, prosta glandins, lipoproteins – composition and function, role in atherosclerosis. Properties of lipd aggregates – micelles, bilayers liposomes and their possible biological functions. Biological membranes. Fluid mosaic model of membrane structure. Lipid metabolism, b - oxidation of fatty acids.
IVAmino acids, Peptides and Proteins
Chemical and enzymatic hydrolysis of proteins to peptides, amino and sequencing. Secondary structure of proteins, forces responsible for holding of secondary structures, a -helix, b - sheets , super secondary structure, triple helix structure of collagen. Tertiary structures of proteins- folding and domain structures. Quaternary structures.
Amino acid metabolism – degradation and biosynthesis of amino acids, sequence determination: chemical / enzymatic / mass spectral , racemization/ detection. Chemistry of oxy tocin and tryptophan releasing hormones (TRH).
Purine and pyramidine bases of nucleic acid, base pairing via H-bonding. Structure of ribonucleic acid (RNA) and di oxyribo nucleic acid (DNA), double helix model of DNA and forces responsible for holding it, an over view of replication of DNA, transcription, translation and genetic code. Chemical synthesis of mono and trinucleoside.
CHE-C 126 Lab Course – Inorganic Chemistry
Qualitative and Quantitative Analysis:
(a). Less Common metal ions – Tl, Mo, W, Ti, Zr, Th, U, (two metal ions in cationic / anionic forms)
(b). Insoluble – oxides, sulphates and halides
(c). Separation and determination of two metal ions Cu-Ni, Ni-Zn, Cu-Fe, Ag-Ni, Ag-Cu etc involving
Volumetric and gravimetric methods.
CHE-C 127 Lab Course – Organic Chemistry
Separation, purification and identification of compounds of Binary mixture preferably one liquid and one solid) using tlc and column chromatography, chemical tests, IR spectra to be used for functional group identification.
Organic Synthesis :
Acetylation of Cholesterol and separation of cholesteryl acetate by column chromatography.
Oxidation : Adipic acid by chromic acid oxidation of cyclohexanol.
Grignard reaction : Synthesis of triphenylmethanol from benzoic acid.
Aldol Condensation : Doibenzal acetone from benzaldehyde.
Sandmeyer reaction , p-chloro toluene and para toluidine
The products be characterized by spectral techniques.
Determination of iodine and saponofication values of an Oil sample
Determination of DO, COD, BOD of water sample.
CHE-C 128 Lab Course – Physical Chemistry
Errors and Analysis and Statistical Data Analysis :
i.Statistical treatment of errors analysis, student’s ‘t’ test , null hypothesis, rejection criteria , F & Q test; Linear regression analysis, curve fitting.
Calibration of Volumetric Apparatus, burette, pipette and standard flasks.
Note : Such exercise be incorporated as practice work while verifying the experimental data.
i.To Study surface tension – concentration relationship for solutions (Gibbs equation).
i.Determination of congruent composition and temperature of a binary system (e.g. diphenylamine-benzophenone system)
ii.Determination of glass transition temperature of a given salt (e.g.CaCl2) conduct metrically.
iii.To construct the phase diagram for three component system (e.g. chloroform – acetic acid – water).
i.Determination of the effect of (a) Change of temperature (b) Change of concentration of reactants and catalyst and (c) Ionic strength of the media on the velocity constant of hydrolysis of an ester / ionic reactions.
ii.Determination of the velocity constants of hydrolysis of an ester / ionic reactions in micellar media.
iii.Determination of the rate constant for the oxidation of iodide ions by hydrogen peroxide studying the kinetics as an iodine clock reaction.
iv.Flowing clock reactions (Ref:: Experiments in Physical chemistry by Showmaker).
v.Determination of the primary salt effect on the kinetics of ionic reactions and testing of the Bronsted relationship (iodide ion is oxidised by persulphate ion).
i.Determination of molecular weight of non-volatile and non-electrolyte /electrolyte by cryoscopy method and to determine the activity coeffieient of an electrolyte.
ii.Determination of the degree of dissociation of weak electrolyte and to study the deviation from ideal behaviour that occurs with a strong electrolyte.
i.Determination of the rate constant for hydrolysis/ inversion of sugar using polarimeter.
ii. Enzyme kinetics – inversion of sucrose
1.Vogel’s Textbook of quantitative Analysis, revised, J. Bassett R. C. Denney, G. H. Jeffery and J. Mendham, ELBS
2.Synthesis and Characterization of Inorganic compounds, W. L. Jolly, Prentice Hall
3.Experiments and Techniques in Organic Chemistry, D. Pasto, C. Johnson and M. Miller, Prentice Hall
4.Macroscale and Microscale Organic Experiments, K. L. Williamson, D. C. Heath.
5.Systematic Qualitative Organic Analysis, H. Middleton, Adward Arnold.
6.Handbook of Organic Analysis-Qualitative and quantitative, H. Clark, Adward Arnold.
7.Vogel’s Textbook of Practical Organic Chemistry, A. R. Tatchell, John Wiley
8.Practical Physical Chemistry, a. M. James and F. E. Prichard, Longman
9.Findley’s Practical Physical Chemistry, B. P. Levitt, Longman
10.Experimental Physical Chemistry, R. C. Das and B. Behera, Tata McGraw Hill.
1.Advanced Inorganic Chemistry, F.A. Cotton and Wilkinson, John Wiley.
2.Inorganic Chemistry, J.E.Huhey, Harpes & Row.
3.Chemistry of Elements, N.N. Greenwood and A Earnshow, Pergamon.