Molecular Symmetry & Spectroscopy : Symmetry elements and operations, Symmetry point groups

of molecules. Terms symbols and their determination for gaseous atom/ions. Spin-orbit coupling in

free ion terms.

Spectroscopy : Theoretical treatment of rotational, vibrational-rotation, electronic and Raman

spectroscopy, Theory of nuclear magnetic resonance, Mossbauer, photoelectron spectroscopy, scanning

tunneling microscopy. Applications of electronic, vibrational, UV-VIS, IR, NMR and Raman

spectroscopy for structural elucidation of compounds and in analysis.

Electrochemistry and Electroanalytical methods : Electrochemical cell equation, EMF of cells with

transference and without transference. Electrode kinetics, electrical double layer, electrode/electrolyte

interface, Mechanism of electrode reactions. Overpotential batterics, primary and secondary fuel cells,

corrosion and corrosion prevention, Ionselective electrodes, controlled potential electrolysis,

voltammetry – polarography, Anodic stripping voltametry, cyclic voltermetry.

Electrochemistry and Polarization : Mechanism of electrode reactions. The current potential relation.

The Tafel equation. Butler-Volmer equation, Concept of hydration number, activities in electrolytic

solutions; mean ionic activity coefficient; Debye-Huckel treatment of dilute electroyte solutions.

Nuclear Chemistry and Radiochemical Analysis: Stability of nucleus, Nuclear reactions,

measurements of nuclear radiations, nuclear energy and nuclear reactors. Neutran activation analysis,

dilution analysis, tracer techniques.

Surface Phenomena : Uni and bimolecular surface reactions. Langmuir-Hnishelwood and Langmuir

Rideal mechanisms. Inhibition ofsurface reactions Absolute reaction rate theory ofsurface reaction.

Chromatographic techniques : Principles, classification and applications of column curomatography,

size exclusion chromatography, ion exchange chromatography, gas chromatography and high

performance liquid chromatography.

Other Physical Techniques : Principle and applications of TGA, DTA and DSC. Atomic Absorption

spectroscopy, Atomic Fluorescence spectroscopy, X-ray Fluoresence Spectroscopy, photoelectron

methods of analysis - Enzyme catalyzed reactions and their applications in chemical analysis,

immunoassay.

Data Analysis: Data reduction, accuracy and precision, determinate and indeterminate errors,

propagation of errors, confidence interval, rejection of results, least squares analysis, hypothesis testing

using statistical analysis.

Intermolecular Forces : Nature of intermolecular forces, Various contribution of intermolecular

forces. London theory of dispersion forces. Potential parameters of L-J potentials and evaluation of

second virial coefficients.

Ideal and non-ideal solutions : Thermodynamic functions of mixing and excess functions, Partial

molar properties of liquid mixtures. Determination of partial molar volume and partial molar enthalpy,

Gibbs-Duhem – Margules equation. Thermodynamics of hydrolysis of adenosine triphosphate (ATP).

Standard Gibbs free energies of a number of phosphate esters. Binding of oxygen by Myoglobin and

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Heamoglobin.

Thermodynamics : Second law of thermodynamics, entropy, Gibbs-Helmoholtz equation. Third law of

thermodynamics and determination of entropy. Free energy and entropy of mixing, partial molar

quantities, Gibbs-Duhem equation. Equilibrium constant, temperature-dependence of equilibrium

constant, phase diagram of one and two component systems, phase rule and its thermodynamics

derivation.

Statistical Thermodynamics : Thermodynamic probability and entropy; Maxwell- Boltzmann,

constants. Theories of specific heat forsolids.

Non-equilibrium Thermodynamics : Postulates and methodologies, liner laws, Gibbs equation,

Onsager reciprocal theory. Entropy production and entropy flow.

Reaction Kinetics : Mechanisms of photochemical chain and oscillatory reactions. Collision theory of

reaction rates; steric factor, treatment of unimolecular reactions. Theory of absolute reaction rates,

comparision of results with Eyring and Arrhenius equations. Ionic reactions: salt effect. Homogeneous

catalysis and michaelis-Menten kinetics; heterogeneous catalysis. Luminesence and Energy transfer

processes. Study of kinetics by stoppedflow technique, relaxation method, flash photolysis and

magnetic resonance method.

Mechanism of Organic Reactions: Labelling and Kinetic isotope, Hamett equation, (sigma-rho)

relationship, non-classical carbonium ions, neighbouring group participation.

Inorganic Reaction and Mechanism : Inert and labile complexes. Ligand displacement reactions in

octahedral and tetrahedral complexes. Trans effect. Mechanism of electron transfer, isomerisation and

recemisation reaction.

Quantum Chemistry : Postulates of quantum mechanics and Schrodinger equation : free particle,

particle in a 3-dimentional box, degeneracy, harmonic oscillator, rigid rotator and the hydrogen atom.

Angular momentum, including spin; coupling of angular momenta including spin-orbit coupling. The

variation method and perturbation theory : Application to the helium atom; antisymmetry and

Exclusion Principle, Slater determinantal wave functions. Terms symbols and spectroscopic

states.Born- Oppenheimer approximation : LCAO-MO and VB treatments of the hydrogen molecule

Hydrogen molecule ion, electron density, forces and their role in chemical binding. Huckel pi-electron

theory and its applications to ethylene, butadiene and benzene. Idea of self-consistent fields.

Macromolecules: Determination of molecular weights. Kinetics of polymerization. Stereochemistry and

mechanism of polymerization.
Solids : Bonding and conduction, Electronic structures of solids, Schottky and Frenkel defects,

Electrical properties; Insulators and semiconductors; superconductors; Free electron theory, Fermi- gas

theory and band theory of solids, Solid-state reactions.

Pericyclic Reactions : Selection rules and stereochemistry of electrocyclic reactions, cycloaddition

reactions and sigmatropic shifts, Cope and Claisen rearrangements.

Common Organic Reactions and Mechanisms : Reactive intermediates, Formation and stability of

carbonium ions, carbanians, carbenes, nitrenes, radicals and arynes. Nucleophilic, electrophilic, radical

substitutions, addition and elimination reactions. Familiar name reactions: Alodol, Perkin, Stobbe,

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Dieckmann condensations; Hofmann, Schmidt, Lossen, Curtius, Beckmamm and Fries rearrangment;

Reimer – Tiemann, Reformatsky and Grignard reactions. Diels – Alder reactions;

Clasien rearrangement; Friedial – Crafts reaction; Wittig reaction; and Robinson annulation. Routine

functional group transformations and interconversions of simple functionalities. Hydroboration,

Oppenaur oxidation; Clemmensen, Wolff-Kishner, Meerwein-Ponndorf-Verley and Birch reductions.

Favorskli reation; Stork enamine reaction; Michael addition, Mannich Reaction; Sharpless asymmetric

epoxidation; Ene reaction, Barton reaction, Hofmann- Loffler-Freytag reaction, Shapiro reaction,

Baeyer-Villiger reaction, Chichibabin reaction.

Reagents in Organic Synthesis : Use of the following reagents in organic synthesis and functional

group transformations; Complex metal hydrides, Gilman’s reagent, lithium diisopropylamide (LDA)

dicyclohexycarbodiimide. 1,3-Dithiane (reactivity umpolung), trimethylsilyl iodide, tri-nbutyltinhybride,

phase transfer catalysts, crown ethers and Merrified resin, Peterson’s synthesis, Wilkinson’s catalyst,

Baker yeast, ylides and enamines.

methane rearrangement, photochemistry of areanes. Photo rearrangements of ά, β unsaturated enones

and dienones.

Aromaticity : Criteria of aromaticity, Aramaticity of ions and annulenes. Construction of pi molecular

orbital energy diagram of aromatic and antiaromatic compounds.

Stereochemistry and conformational Analysis : Recognition of symmetry elements and chiral

structures; R-S nomenclature, diastereosiomerism in acyclic and cyclic systems; E-Z isomerisms,

conformational analysis of cyclic (chair and boat cyclohexanes) and acyclic systems. Interconversion of

Fischer, Newman and Sawhorse projections. Newre method of asymmetric synthesis (including

enzymatic and catalytic nexus), enantio and diastereo selective synthesis. Effects of conformation on

reactivity in acyclic compounds and cyclohexanes.

Coordination Chemistry : Crystal field, ligand field and molecular orbital theories, crystal field

splitting of d-orbitals, CFSE, Interpritation of electronic spectra of coordination compounds using

Orgel digrams. Calculation of Racahparameter (B’) and nephelanxdatic ratio β foroctahedral d2/d8 and

tetrahedral d2/d7 3d metal complexes. Magnetic properties of 3d metal complexes with A, E and T

crystal field ground terms, calculation of effective magnetic moment. Orbital contribution to the

magnetic moment, spin-orbit coupling, high spin-low spin equilibria. Mononuclear and polynuclear

metal carbonyls. Structureand bonding in metal carbonyls and nitrosyls.

Oranometallic Chemistry : Classification of organometallic compounds based on hapiticity

andpolarity of M-C bond, nomenclature and general characteristics. General methods of preparation
and

important reactions of transition metal Λ- complexes of unsatural hydrocarbons such as alkenes,

allyl, cyclopentadiene and arene. Organometalics in organic synthesis and in homogeneous catalytic

reactions (hydrogenation, hydrofomaylation, isomerisation). Activation of small molecules by

coordination.
Chemistry of Lanthanides and Actinides: Oxidation states and coordination numbers, spectral and

magnetic properties; Ion exchange sepration, use of lanthanide compounds as shift reagents.

Bioinorganic and Bioorganic Chemistry : Metal ions in biological system, Function, Structure and

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bonding of hemoglobin and myoglobin, molecular mechanism of ion transport across membranes;

ionophores. Photosynthesis, PSL, PSH; nitrogen fixation, oxygen uptake proteins, cytochromes.

Elementary structure and function of biopolymers such as proteins and nucleic acids.

Chemistry of Non-transitional Elements: General discussion on the properties of the nontransition

elements; special features of individual elements; synthesis, properties and structure of their halides
and

oxides, polymorphism of carbon, phosphorus and sulphur. Synthesis, properties and structure of

boranes, carboranes, borazines, silicates carbides, silicones, phosphazenes, sulphur – nitrogen

compounds: peroxo compounds of boron, carbon and sulphur; oxy acids of nitrogen, phosphorus,

sulphur and halogens, interhalogens pseudohalides and noble gas compounds.

Chemistry of Transition Elements: Coordination chemistry of transition metal ions; Stability

constants of complexes and their determination; stabilization of unusual oxidation states.

Stereochemistry of coordination compounds. Ligandfield theory, splitting of d-orbitals in lowsymmetry

transfer spectra; spectro chemical series, nephelauxetic, series Magnetism: Dia-para-ferro and

antiferromagnetism, quenching of orbital angular moment, spinorbit coupling, inorganic reaction

mechanisms; substitution reactions, trans effect and electron transfer reactions, photochemical reaction

of chromium and ruthenium complexes. Fluxional molecules iso and heteropolyacids; metal clusters.

Spin crossover in coordination compounds.