Note: The students have to appear in four elective theory papers and one practical paper which includes seminar presentation. They have to select at least one paper from each group. The fourth elective could be from any group.
Group - A
Group - B
Group - C
Organotransition Metal Chemistry
Advanced Quantum Chemistry
Bioinorganic and Supramolecular Chemistry
Nuclear and Radiochemistry
Chemistry of Natural Products
Organometalls in organic synthesis & Coordination Chemistry
Seminar on allotted topics (Instructions)
Semester – I
Paper - I Inorganic Chemistry
Symmetry and group Theory in chemistry:
Symmetry element and operation, definition of mathematical group, sub group, cyclic group, conjugacy relation and classes, point symmetry group (Schonflies symbols), use of point group symmetry : optical activity, dipole moment, representation of group by matrices, character of representation, the great orthogonality theorem (without proof) and its importance, irreducible representation, character table and their use.
Stereochemistry and Bonding in main group compounds:
VSEPR, Walsh diagrams (tri-and penta-atomic molecules), dπ-pπ bonds, Bent rule and energetics of Hybridization, some simple reaction of covalently bonded molecules.
Limitation of crystal field theory, Molecular orbital theory, Octahedral, tetrahedral and square planar complexes, π-bonding and molecular orbital theory.
Electronic Spectra and magnetic properties of transition metal complexes:
Spectroscopic ground states, correlation, Orgel and Tanabe-Sugano diagram for transition metal complexes (d1 –d9), calculation for Dq, and b parameter, charge transfer spectra, spectroscopic method for assignment of absolute configuration in optically active metal chelates and their stereochemical information, anomalous magnetic moments, magnetic exchange coupling and spin crossover.
Isopoly and Heteropoly acid and salts of V, Mo, W.
Paper - II Organic Chemistry
Nature of bonding in organic molecules:
Delocalized chemical bonding-conjugation, cross conjugation, resonance, hyperconjugation, bonding in fullerenes, tautomerism. Aromaticity in benzenoid and non-benzenoid compound, alternate and nonalternate hydrocarbon, Huckel rule, energy of p-molecular orbital, annulenes, antiaromaticity, Ψ−aromaticity homoaromaticity, PMO approach. Bond weaker than covalent-addition compound, crown ether complexes and cryptands, inclusion compound, cyclodextrins, catenanes and rotaxane.
Conformational analysis of cycloalkanes, declines, effect of conformation on reactivity, conformation of sugars, steric strain due to unavoidable crowding. Element of symmetry, chirality, molecules with more than one chiral center, thro and erythro isomer, methods of resolution, optical purity, enantiotopic and diastereotopic atoms, group of faces, stereospesific and stereoselective synthesis, asymmetric synthesis, optical activity in absence of chiral carbon (biphenyls, allenes and spiranes), chirality due to helical shape. Stereochemistry of compound containing nitrogen, sulphur and phosphorous.
Reaction mechanism: structure and reactivity:
Types of mechanism, types of mechanism, thermodynamics and kinetic requirements, kinetic thermodynamic control, Hammonds postulate, Curtin-hammett principle. Potential energy diagram, transition state and intermediates, methods of determining mechanism, isotope effect. Hard and soft acids and bases. Generation, structure, stability and reactivity of carbocations, carbanions, free radicals, carbenes Effect of structure on reactivity – resonance and field effect, steric effect, quantitative treatment. The Hammett equation and linear free energy relationship, substituent and reaction constants, Taft equation.
Aliphatic nucleophilic substitution :
The SN2, SN1 and SET mechanism.
The neighboring group mechanism, neighboring group participation by π and bond, anchimeric assistance.
Classical and nonclassical carbocations, phenonium ions, norboryl system, common carbocation rearrangement. Application of NMR spectroscopy in detection of carbocations.
The SN1 mechanism
Nucleophilic substitution at an allylic, aliphatic trigonal and vinylic carbon.
Paper - III Physical Chemistry
Theory of reaction rate: collision, activated complex and unimolecular reaction i.e. Lindemann and preliminary ideas (Hinshelwood, Rice Ramopereger and RKKM theories), thermodynamics of reaction rate.
The ideas of reaction kinetics in solution with special reference to kinetic salt effects.
The fast reaction kinetics, fundamental aspects of NMR, Relactation methods, flow and flesh photolysis. Preliminary ideas of molecular reaction dynamics.
Simple ideas of Oscillatory chemical reaction, belosov- Zhabotinsky reaction.
Photochemical reaction: Chain reaction involving Hydrogen Chlorine, Hydrogen- bromine reaction and pyrolysis if acetaldehyde. Kinetics of enzyme reaction.
Surface tension, capillary action , pressure difference across curved surface (Laplace equation), vapor pressure of droplets (Kelvin equation), Gibbs adsorption isotherm, estimation surface area (BET equation), surface film of liquids (electro –kinetic phenomenon ), catalytic activity at surface.
Surface active agent, classification of surface active agent, micellization, hydrophobic interaction, critical micellar concentration (CMC), factors affecting the CMC of surfactant, counter ion binding to micelles, thermodynamics of micellization – phase separation and moss action models , solubilization, micro emulation, reverse micelles.
Polymer –definition, classification of polymer, electrically conducting , five resistant, liquid crystal polymer, kinetics and mechanism of polymerization (Chain reaction and step growth), molecular mass, number and mass average molecular mass, molecular mass determination (Osmometry, diffusion and light scattering methods),sedimentation, chain configuration of macromolecules, calculation of average dimensions of various chain structures.
Activity, activity coefficient, Debye-Huckel theory for electrolytic solution, determination of activity and activity coefficient, ionic strength.
Electrochemistry of solution, Debye-Huckel – Onsager treatment and its extension, ion solvent interaction, Debye Huckel, B Jerum mode.
a. Qualitative analysis of inorganic mixture of 8 radicals containing not more than two of the following less common metals: Tl, Mo, W, Zr, Th, V, U.
b. Insoluble – oxides, sulfates and halides.
Separation of cations and anions by
a. Paper chromatography
b. Column chromatography- Ion exchange.
Separation , Purification and identification of compound of two component mixture using the and column chromatography, chemical tests. IR spectra to be used for functional group identification.
Determination of percentage or number of hydroxyl group in an organic compound by acetylation method.
Estimation of amines/phenols using bromate bromide solution/or acetylation method.
Determination of iodine and saponification value of an oil sample.
Determination of DO, COD and BDO of water sample.
Error and statistical data analysis
Calibration of fractional weights.
Calibration of volumetric apparatus-burette, pipette and standard flask.
Determine the cell constant of a given conductivity cell at a given temp.
Determine the equivalent conductance of a strong electrolyte at several concentration at a given temperature and test the validity if Onseger’s equation .
By potentiometer taking C1 and C2 (i) same concentration (ii) Different concentration and hence to see the effect of dilution
Determine the solubility of a sparingly soluble salt in water by EMF method.
Determination of the strength of strong and week acid in a given mixture by using pH –meter.
Determination of the rate constant and order of reaction for the hydrolysis of the methyl acetate catalyzed by an acid at different ionic strengths at a given temp.
Determine the rate constant of hydrolysis of an ester in m iceller media at a given temperature.
Determination of apparent molecular weight of an electrolyte in water and hence calculate the Vant Hoff factor and degree of dissociation of the electrolytes by cryoscopic method.
Determination of degree of dissociation / hydrolysis of weak electrolyte by cryoscopic method.
To study the adsorption of oxalic acid on activated charcoal and test the validity of Freundlich/ Langmuir adsorption isotherm.
To study the distribution of I2 betweenCCl4 and calculate the partition coefficient .
Determination of the partition coefficient of benzoic acid between water and benzene and comment on the molecular stat of benzoic acid in benzene.
Semester – II
Paper - I Inorganic Chemistry
Metal ligand equilibria in solution:
Stepwise and overall formation constant, tends in stepwise constant, factor affecting the stability if metal complex with reference to the nature of metal ion and ligand, chelate effect and its thermodynamic origin.
Reaction mechanism of transition metal complexes:
Energy profile of reaction, reactivity of metal complexes, inert and labile complexes, kinetics of octahedral substitution, substitution of square planar complexes, the trans effect, mechanism of the substitution reaction, redox reaction, electron transfer reaction, outer sphere type reactions, cross reaction and Marcus-Hush theory, inner sphere type reaction.
Organoberyllium and silicon compounds: preparation stability and important reaction of transition metal alkyl and aryls. Metal carbonyls – reactions, structure and bonding, vibrational spectra of metal carbonyls for structural elucidation.
Higher boranes, carboranes, metalloboranes and metallocarboranes.
Metal carbonyls and halide clusters.
Compounds with metal-metal multiple bonds
Classification of molecules, rigid rotor model, effect of isotopic substitution on the transition frequency, intensities, non-rigid rotor. Stark effect, nuclear and electron spin interaction and effect of external field. Applications.
Infra red spectroscopy:
Review of linear harmonic oscillator, vibrational energies of diatomic molecules, zero point energy, force constant and bond strength, vibration of polyatomic molecules, selection rules, normal modes of vibration, group frequencies, overtones, hot bands, factor affecting the band position and intensities, Far IR region metal ligand vibrations, normal coordinate analysis.
Classical theories of Raman effect. Pure vibrational, vibrational-rotational Raman spectra, selection rule, mutual exclusion principle. Resonance Raman spectroscopy, Coherent Anti Stocks Raman spectroscopy (CARS).
Paper - II Organic Chemistry
Aromatic Electrophilic substitution:
The arenium ion mechanism, Orientation and reactivity, energy profile diagram. The ortho / para ratio, ipso attack, orientation in other ring system, quantitative treatment of reactivity in substrates and electrophiles. Diazonium coupling, Vilsmeir reaction, Gatterman-Koch reaction.
Aromatic Nucleophilic substitution:
The SNAr, SN1, benzyne and SRN1 mechanisms. Reactivity-effect of substrates structure, leaving group and attacking nucleophile. The Von Richter, Sommelet – Houser and Smiles rearrangements.
Free Radical Reactions:
Types of free radical reactions, free radical substitution mechanism, mechanism at an aromatic substrate, neighboring group assistance. Reactivity for aliphatic and aromatic substrates at a bridgehead. Reactivity in attacking radicals. The effect of solvent on reactivity.
Alicyclic halogenation (NBS), oxidation of aldehyde to carboxylic acid, auto-oxidation, coupling of alkynes and arylation of aromatic compounds by diazonium salt. Sandemeyer reaction. Free radical rearrangement. Hunsdiecker reaction.
Addition to Carbon – Carbon multiple bonds:
Mechanistic and stereochemical aspects of addition reaction envolving electrophiles. Nucleophiles and free radicals , ragio-and chemoselectivity, orientation and reactivity. Addition to cyclopropane ring. Hydrogenation of double and triple bonds, Hydrogenation of aromatic ring. Hydroboration. Michaels reaction. Sharpless asymmetric epoxidation.
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, Organozinc and organolithium reagents to carbonyl and unsaturated carbonyl compounds. Witting reaction.
Mechanism of condensation reaction involving enolates-aldol, Knoevenagel, Claisen, Mannich, Benzoin, Perkin and Sotobbe reaction.
Hydrolysis of ester and amides, ammonolysis of esters.
The E2, E1 and E1cB mechanism and their spectrum. Orientation of double bond. Reactivity-effects of substrates structures, attacking base, the leaving group and the medium.
Mechanism and orientation in pyrolytic elimination.
Magnetic Resonance Spectroscopy:
Nuclear Magnetic Resonance Spectroscopy:
Nuclear spin, nuclear resonance, saturation, shielding of magnetic nuclei, chemical shift and its measurement, factors influencing chemical shift, deshielding, spin-spin interaction, factor influencing coupling constant ‘J’. Classification (ABX, AMX, ABC, A2B2 etc.), spin decoupling, basic ideas about instrument, NMR studies of nuclei other than proton-13C, 19F and 31P, FT NMR, advantage of FT NMR, use of NMR in medical diagnostics.
Electron Spin Resonance Spectroscopy:
Basic principles, zero field splitting and Kramers degeneracy, factor affecting the “g” value. Isotopic and anisotopic hyperfine coupling constant, spin Hamiltonian, spin densities and McConnell relationship, measurement techniques, applications.
Nuclear quadrupole resonance spectroscopy
Quadrupole nuclei, quadrupole moments, electric field gradient , coupling constant, splitting.
Energy level, molecular orbital, vibronic transition, vibrational progressions and geometry of the exited states, Franck-Condon principle, electronic spectra of the polyatomic molecules. Emission spectra, radiativ and nonradiativ decay, internal conversion, sctra of transition metal complexes, charg-transfer spectra.
Paper - III Physical Chemistry
Introduction to exact quantum Mechanical Results:
The Schrodinger equation and the postulates of quantum mechanica. Discussion of solution of the Schrodinger equation to the some medel system viz. particle in abox, the harmonic oscillator, the rigid rotor, the hydrogen atom.
The variation theorem, linear variation principle. Perturbation theory (first order and non- degenerate). Simple application of variation method and perturbation theory.
Ordinary angular momentum, eigenfuctions for angular momentum, eigenvalues of angular momentum.
Electronic structure of atom:
Electronic configuration, Russell-Saunders term and coupling schemes, Slater-Condon parameter, term separation energy of pn configuration, term separation energy for the dn configuration, magnetic effects: spin-orbit coupling and Zeeman splitting.
Molecular Orbital Theory:
Huckel theory of conjugated system, bond order and charge density calculation. Application to ethylene, butadiene etc. Introduction to extended Huckel theory.
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 the time dependent perturbation theory, transition moment, selection rules, intensity of spectral line, born-Oppenheimer approximation, rotational, vibrational and electronic enery level.
Brief resume of concepts of low of thermodynamics, free energy, chemical potential and entropy. Partial molar quantities and their physical significance. Concepts of fugacityand determination of fugacity. Application of phase rule to three component system, second order phase transition.
Concepts of distribution, thermodynamic probability and most probable distribution. Ensemble averaging. Canonical, grand canonical and microcanonical ensembles, corresponding distribution law (usingLgrang”s methods of undetermined multipliers.)
Partition fuctions- translational, rotational, vibrational and electronic parttion fution,calculation of thermodynamic propertiesin the term of partition function. Application ofpartition function. Heat capacity behavior of solid- chemical equilibrium and equilibrium constant in the term of partition function.
Non Equilibrium Thermodynamics:
Thermodynamic criteria for non – equillibrium stat, etropy production and entropy flow, entropy balance equation for different irreversible processes (e.g. heat flow , chemoical reaction etc.) transformation of generalized fluxed and forces, non equilibrium stationary states, phenomenological equation, microscopic reversibility and Onager’s reciprocity relation, electrokinetic phenomena, diffusion, electric conduction, irreversible thermodynamics for biological system, coupled reaction .
Thermodynamics of electrified interface equation, deviation of electro-capillarity, Lippmann equation (surface excess), methods of determination, structure of electrified interfaces. Guoy Chapman, Stern, Bockris, Devanathan method.
Over potential, exchange current density, deviation of Butler- Volmer, Tafel plot.
Electrocatalysis – Influence of various parameters, Hydrogen electrode.
Nernst-Planck equation, electrocardiography.
Polarography theory, likovic equation, half wave potential and its significant.
Introduction to corrosion, homogenous theory, form of corrosion, corrosion monitoring and prevention Methodism.
Separation and determination of two metal ion Cu-Ni, Cu-Zn., Cu-Fe etc. involving volumetric and gravimetric methods.
Preparation and their characterisation
Preparation of selected inorganic compound and their studies by I.R., electronic spectra, Mossbaure, E.S.R. and magnetic susceptibility measurements. Handling of air and moisture sensitive compound.
Prussian Blue, Turnbull’s Blue
Organic synthesis :
Acetylation: Acetylation of cholesterol and separation of cholesteryl acetate by column chromatpgraphy.
Oxidation: Adipic acid by chromic acid oxidation of cyclohexenol.
Grignard reaction: Synthesis of triphenylmethenol from benzoic acid.
Aldol condensation: Dibenzal acetone from benzaldehyde.
Sandmeyer reaction: p- Chlorotoluence from p- toluidne.
Acetoacetic ester Condensation: Synthesis of etyle –n-butylacetoacetate by A.EE. condensation.
Cannizzaro reaction: 4- Chlorobenzaldehyde as substrate.
Friedel crafts reaction: B-Benzoyl propionic acid from succinic anhydride and benzene.
Aromatic electrophilic substitution: Synthesis of p- nitroaniline and p-bromoaniline
Note : The product may be characterized by spectral techniques.
Error and statistical analysis
Draw a straight line using method of least squares from given data.
Test the validity of student s t test by F-test approach.
Determine the equivalent conductance of a weak electrolyte at different concentration and hence test the validity of Ostwald’s dilution Law. Also determine the dissociation constant Ka/Kb of the weak electrolyte
Deter the solubility of sparingly soluble substance in water at given temperature by conductance method.
Detremine the EMF of a given a concentration cell by potentiometer and find out the effect of dilution on the EMF of cell.
Determine the pH a given buffer solution using given hydrogen electrode.
Determination of dissociation constant of monobasic/polybasic acid using pH meter.
Dtermine the velocity constant and order of reaction for hydrolysis of ethyl acetate by sodium hydroxide at given temperature (saponification of an ester)
Study of kinetics of iodine clock reaction.
Determine the apparent molecular weight of non electrolyte cryscopically.
Study of association of benzoic acid in benzene by cryoscopic method.
Construct the phase diagram for three component system (eg. ethanol, benzene and water or chloroform, acetic acid and water).
Determine the rate constant for inversion of cane – suger using a polarimeter.
Find the specific rotation and molecular rotation of cane – suger polarimetrically and also find the concentration of unknown solution.
Semester – III
Applications of Spectroscopy
Electron Spin Resonance Spectroscopy
Hyperfine Coupling, spin polarization for atoms and transition metal
ions, spin-orbit coupling and significance of g-tensors, application to
transition metal complexes (having one unpaired electron) including
biological systems and to inorganic free radicals such as PH4, F2-and [BH3]-.
Nuclear Magnetic Resonance Spectroscopy
Ap Applications of multinuclear NMR with emphasis on 11B, 19F, 31P, 125Te, 119Sn and 195Pt NMR.
Basic Principles, spectral parameters and spectrum display. Application of the technique to the studies of (1) bonding and structures of Fe+2 and Fe+3 compounds including those of intermediate spin, (2) Sn+2 and Sn+4 compounds – nature of M-L bond, coordination number, structure and (3) detection of oxidation state and in equivalent MB atoms.
Metal Ions in Biological Systems
Essential and trace metals.
Vitamin B12, methyl cobalamine, Biomethylation.
Heme proteins and oxygen uptake, structure and function of hemoglobin, myoglobin, homocyanins and hemerythrin, model synthetic complexes of iron, cobalt and copper
Electron Transfer in Biology
Structure and function of metalloproteins in electron transport processes-cytochromes and ion- sulphur proteins, synthetic models.
Biological nitrogen fixation, molybdenum nitrogenase, spectroscopic and other evidence, other nitrogenases model systems.
Environmental Chemistry 16 Hrs
Aquatic pollution: water quality parameters viz. dissolved oxygen, biochemical oxygen demand, heavy metals Cl-, SO4 2-, NO3-, PO4 3- contents.
Industrial pollution, viz. cement, sugar, distillery, drug, paper and pulp, thermal power plants, metallurgy.
Domestic pollution viz. sewage, detergents, oil pollutants and its management
Chemistry of less familiar metals: Os, Ir, Ru, Rh, Pd,
Platinium phosphine complexes
General method of preparation and important reactions (insertion reactions, metathetical reactions , Lewis acid-base reactions, reactions with protic compounds) of metal and metalloid amides .
Preparation of important radio isotopes (1H3, 6C14, 11Na22, 15P32, 16S35) and applications of coordination compounds of Tc99 as imaging agents in Nuclear Medicine.
Principle, instrumentation and applications of TGA and DTA Ion exchange- preparation, mechanism, of exchange capacity of ion exchangers, Principle and applications of photometric and colorimetric techniques in inorganic analysis.
Applications of Spectroscopy:
Ultraviolet and Visible Spectroscopy
Various electronic transitions (185-800 nm), Beer-Lambert Law, effect of solvent on electronic transitions, ultraviolet bands for carbonyl compounds, unsaturated carbonyl compounds, dienes,conjugated polyenes. Fieser-Woodward rules for conjugated dienes and carbonyl compounds, ultraviolet spectra of aromatic and heterocyclic compounds. Steric effect in biphenyls.
Instrumentation and sample handling. Characteristic vibrational frequencies of alkanes, alkenes, alkynes, aromatic compounds, alcohols, ethers, phenols and amines. Detailed study of vibrational frequencies of carbonyl compounds (ketones, aldehydes, esters, amides, acids, anhydrides, lactones, lactams and conjugated carbonyl compounds). Effect of hydrogen bonding and solventeffect on vibrational frequencies, overtones, combination bands and Fermi resonance. FTIR. IR of gaseous, solids and polymeric materials.
Optical Rotatory Dispersion (ORD) and Circular Dichroism (CD)
Definition, deduction of absolute configuration, octant rule for ketones.
Nuclear Magnetic Resonance Spectroscopy
General introduction and definition, chemical shift, spin-spin interaction, shielding mechanism, mechanism of measurement, chemical shift va lues and correlation for protons bonded to carbon (aliphatic, olefinic, aldehydic and aromatic) and other nuclei (alcohols, phenols, enols, carboxylic acids, amines, amides & mercapto), chemical exchange, effect of deuteration, complex spinspin interaction between two, three, four and five nuclei (first order spectra), virtual coupling. Stereochemistry, hindered rotation, Karplus curve-variation of coupling constant with dihedral angle. Simplification of complex spectra-nuclear magnetic double resonance, contact shift reagents, solvent effects. Fourier transform technique, nuclear Overhauser effect (NOE).
Carbon-13 NMR Spectroscopy
General considerations, chemical shift (aliphatic, olefinic, alkyne, aromatic, heteroaromatic and carbonyl carbon), coupling constants.
Two dimension NMR spectroscopy – COSY, NOESY, DEPT, INEPT, APT and INADEQUATE techniques.
Introduction, ion production – El, Cl, FD and FAB, factors affecting fragmentation, ion analysis, ion abundance. Mass spectral fragmentation of organic compounds, common functional groups, molecular ion peak, metastable peak, McLafferty rearrangement. Nitrogen rule. High resolution mass spectrometery. Examples of mass spectral fragmentation of organic compounds with respect to their structure determination.
Photochemistry of Alkenes
Intramolecular reactions of the olefinic bond – geometrical isomerism, cyclisation reactions, rearrangement of 1, 4 – and 1, 5 – dienes.
Photochemistry of Carbonyl Compounds 8 hrs.
Intramolecular reactions of carbonyl compounds – saturated, cyclic and acyclic, b, g-unsaturated and a,b-unsaturated compounds. Cyclohexadienones. Intermolecular cyloaddition reactions – dimerisations and oxetane formation.
Bioorganic Chemistry :
Introduction and historical perspective, chemical and biological catalysis, remarkable properties of enzymes like catalytic power, specificity and regulation. Nomenclature and classification, extraction and purification. Fischer’s lock and key and Koshland’s induced fit hypothesis, concept and identification of active site by the use of inhibitors, affinity labeling and enzyme modification by site-directed mutagenesis. Enzyme kinetics, Michaelis-Menten and Lineweaver-Burk plots, reversible and irreversible inhibition.
Mechanism of Enzyme Action
Transition-state theory, orientation and steric effect, acid-base catalysis, covalent catalysis, strain or distortion. Examples of some typical enzyme mechanisms for chymotrypsin, ribonuclease, lysozyme and carboxypeptidase A.
Kinds of Reactions Catalysed by Enzymes
Nucleophilic displacement on a phosphorus atom, multiple displacement reactions and the coupling of ATP cleavage to endergonic processes. Transfer of sulphate, addition and elimination reactions, enolic intermediates in isomerization reactions, b-cleavage and condensation, some isomerization and rearrangement reactions. Enzyme catalyzed carboxylation and decarboxylation.
Cofactors as derived from vitamins, coenzymes, prosthetic groups, apoenzymes. Structure and biological functions of coenzyme A, thiamine pyrophosphate, pyridoxal phosphate, NAD+, NADP+, FMN, FAD, lipoic acid, vitamin B12. Mechanisms of reactions catalyzed by the above cofactors.
Host-guest chemistry, chiral recognition and catalysis, molecular recognition, molecular asymmetry and prochirality. Biomimetic chemistry, crown ethers, cryptates. Cyclodextrins, cyclodextrinbased enzyme models, calixarenes, ionophores, micelles, synthetic enzymes or synzymes.
Biotechnological Applications of Enzymes
Large-scale production and purification of enzymes, techniques and methods of immobilization of enzymes, effect of immobilization on enzyme activity, application of immobilized enzymes, use of enzymes in food and drink industry-brewing and cheese-making, syrups from corn starch, enzymes as targets for drug design. Clinical uses of enzymes, enzyme therapy, enzymes and recombinant DNA technology.
(ii) Carbohydrate Chemistry :
Structure, function, configuration & conformation of important derivatives of monosaccharides & glycosides; disaccharides (lactose, maltose and sucrose); Polysaccharides – structural polysaccharide (cellulose, chitin); storage polysaccharides (starch and glycogen).
Role of sugars in biological recognition.
Blood group determinants.
Bioethanol from cellulose.
Solid State Chemistry:
Solid State Reactions
General principles, experimental procedures, co-precipitation as a
precursor to solid state reactions, kinetics of solid state reactions.
Crystal Defects and Non-Stoichiometry
Perfect and imperfect crystals, intrinsic and extrinsic defects – point defects, line and plane defects, vacancies-Schottky defects and frenkel defects. Thermodynamics of Schottky and Frenkel defect formation, colour centers, non-stoichiometry and defects.
Electronic Properties and Band Theory
Metals, insulators and semiconductors, electronic structure of solids- band theory, band structure of metals, insulators and semiconductors. Intrinsic and extrinsic semiconductors, doping semiconductors, p-n junctions, super conductors. Optical Properties – Optical reflectance, photoconductionphotoelectric effects. Magnetic Properties – Classification of materials: Quantum theory of paramagnetics- cooperative phenomena- magnetic domains, hysteresis.
Electrically conducting solids, organic charge transfer complex, organic metals, new superconductors.
Interaction of electromagnetic radiation with matter, types of excitations, fate of excited molecule, quantum yield, transfer of excitation energy.
Determination of Reaction Mechanism
Classification, rate constants and life times of reactive energy states – determination of rate constants of reactions. Effect of light intensity on the rate of photochemical reactions. Types of photochemical reactions – photo-dissociation, gas-phase photolysis.
Energy States of Molecules
Phosphorescence and the triplet state, Delayed Fluorescence, Energy level diagrams, Intersystem crossing (Jablonski diagram), Franck – Condon Principle, Physical properties of excited molecules, Light emission and chemical reaction from excited states, Radiationless deactivation of excited states, Application of classical kinetics and thermodynamics to photochemical reactions, Energetic feasibility of a reaction.
Photoreductions, Photo oxidations, Electron transfer reactions, Photoconduction, Chemiluminiscence, Atom sensitized reactions, sensitization and quenching, Photosensitization, Stern – Volmer equation. Photosynthesis, Photomorphogenesis and Photochemistry of vision.
Spectrometry, Actinometry, Flash Photolysis and Laser Beam.
Biological Cell and its Constituents
Biological cell, structure and functions of proteins, enzymes, DNA and RNA in living systems. Helix coil transition.
Standard free energy change in biochemical reactions, exergonic, endergonic. Hydrolysis of ATP, synthesis of ATP from ADP.
Statistical Mechanics in Biopolymers
Chain configuration of macromolecules, statistical distribution end to end dimensions, calculation of average dimensions for various chain structures. Polypeptide and protein structures, introduction to protein folding problem.
Forces involved in biopolymer interactions . Electrostatic charges and molecular expansion, hydrophobic forces, dispersion force interactions. Multiple equilibria and various types of binding processes in biological systems. Hydrogen ion titration curves.
Thermodynamics of Biopolymer Solutions
Thermodynamics of biopolymer solutions, osmotic pressure, membrane equilibrium muscular contraction and energy generation in mechanochemical system.
Cell Membrane and Transport of Ions
Structure and functions of cell membrane, ion transport through cell membrane, irreversible thermodynamic treatment of membrane transport. Nerve conduction.
Biopolymers and their Molecular Weights
Evaluation of size, shape, molecular weight and extent of hydration of biopolymers by various experimental techniques. Sedimentation equilibrium, hydrodynamic methods, diffusion, sedimentation velocity, viscosity, electrophoresis and rotational motions.
Applications of Diffraction Methods in Biopolymers
Gravimetric estimations of complex mixtures involving two or three constituents, Analysis of alloys and minerals.
DTA titrations - Determination of Zn, Ca, Mg and Fe, Hardness of water.
KBrO3 and KIO3 titrations –Determination of As2O3 and [Fe(CN)6]4-.
Chloramine T – titrations - Determination of NO2 in a sample.
Ceric Sulphate titrations - Determination of Fe and Organic acids.
Systematic, separation, purification & identification of the components of a mixture of three organic compounds.
Multi step synthesis of organic compounds.
Extraction of organic compounds.
To verify Freunlich Adsorption Isotherm.
To deternine enthalpy of given salt solution.
To determine molecular weight of a given electrolyte by elevation in boiling point method and also find out its Van’t Hoff factor.
Determine molecular weight of a given polymer by viscosity method.
Find out surface tension, molecular energy and Parachor of a given liquid at room temprature.
Determine molecular weight of a given electrolyte by depression in freezing point method.
Characterization of the complexes by spectroscopic (Vis./IR) measurements.
Measurement of e.m.f. with thermocouple.
Study reaction kinetics between KI and K2S2O3 by fractional change method and find out its order of reaction at room temprature.
Study reaction kinetics between acetone and iodine by isolation method and determine it order of reaction at room temprature.
Determine partial molar volume of solute (eg. KCl) in binary mixture of solvents/mixed solvents system.
Determine temperature dependence of solubility of a compound in two solvents having similar intermolecular interaction – (Benzoic Acid in water and in DMSOwater mixture) and calculate the partial molar heat of solution.
Theory Lab. Course Lectures to be conducted in Semester – III only.
Notations used in an electric circuit, study of electronic components and colour codes, conversion of chemical quantities into electrical quantities. Transducer, illustration with electrodes, thermocouples and thermistors. Passive components: Resistors, capacitors and inductors. Net works of resistors. Thevenin’s theorem, superposition theorem, loop analysis, R C circuits, L R circuits, LCR circuits. Illustration of the use of the circuits in NQR spectroscopy, Mossbauer spectroscopy, cyclic voltametry and in power supplies as filter circuits.
Introduction to ordinary diodes and Zener diodes with some emphasis on p-n junction as a solid state property. Use of diodes as rectifiers, Power supplies.
Transistors: p-n-p and n-p-n transistors. Characteristics of transistors, hybrid parameters; transistor circuits as amplifiers.
Detail of Electives
Group – A
Paper – I Organotransition Metal Chemistry
Compounds of Transiotion Metal-Carbon Multiple bonds:
Alkylidenes, alkylidynes, low valent carbenes and carbines – synthesis, nature of bonds, structural characteristics, nucleophilic and electrophilic reactions on the ligands.
Transition Metal ð–Complexes
Transition metal ð–Complexes with unsaturated organic molecules: alkenes, alkynes, allyl, dienes, dienyl and arene complexes – preparations, properties, nature of bonding and structural features. Important reactions related to nucleophilic and electrophilic attack on ligands.
Transiotion Metal Compounds with Bonds to Hydrogen:
Covalent hydrides : synthesis and important reactions.
Transiotion Metal Compounds with Bonds to Carbon in Catalysis:
General idea of important catalytic steps: ligand coordination and dissociation, insertion and elimination, nucleophilic attack on coordinated ligands, oxidative addition and reductive elimination reactions.
Hydrogenation of alkenes using Wilkinson’s catalyst, Hydroformylation of alkenes using Co and Rh catalysts, Carbonylation of methanol to acetic acid (Monsanto process), Oxidation of alkenes (Wacker process)
Fluxional Organometallic Compounds:
Fluxionality and dynamic equillibria in compounds such as ç2-olefine, ç3- allyl and dienyl complexes.
Organometallic Compounds of Lanthamides and Actinides:
Methods of preparation, properties and structural features.
Paper - II Bioinorganic and Supramolecular Chemistry:
Metal Storage Transport and Biomineralization
Ferritin, transferring and siderophores.
Calcium in Biology
Calcium in living cells, transport and regulation, molecular aspects of intramolecular processes, extracellular binding proteins.
Zinc enzymes – carboxypeptidase and carbonic anhydrase. Iron enzymes – catalase, peroxidase and cytochrome P-450. Copper enzymes – superoxide dismutase. Molybdenum oxatransferase enzymes – xanthine oxidase. Coenzyme vitamin B12.
Metal – Nucleic Acid Interactions
Metal ions and metal complex interactions, Metal complexes –nucleic acids.
Metals in Medicine
Metal deficiency and disease, toxic effects of metals, metals used for
diagnosis and chemotherapy with particular reference to anticancer drugs.
Concepts and language.
Molecular recognition: Molecular receptors for different types of molecules including arisonic substrates, design and synthesis of coreceptor molecules and multiple recognition.
Supramolecular reactivity and catalysis.
Transport processes and carrier design.
Supramolecular devices. Supramolecular photochemistry, supramolecular electronic, ionic and switching devices. Some example of self-assembly in supramolecular chemistry.
Paper - III Nuclear and Radiochemistry
Nuclear stability, binding energy, n-p radio, Meson theory of nuclear forces, Structure of the nucleus, Liquid drop model, Nuclear shell model, Magic numbers, Radioactive decay and Radioactive series, The basic principles of Geiger Miiller counter and proportional counter.
Energetics of nuclear reactions based on conservation of angular momentum, coulombic repulsion, potential barrier, particles escalation through electrostatic Van de Graaff generator, multiple stage linear accelerators, Cyclotrons, frequency modulated cyclotrons and synchrocyclotrons
Cross Section, Resonance and tunnelling, Types of nuclear reactions, Nuclear reactions induced by neutrons, protons, deuterons, alpha particles, g- photons and accelerated heavy charged ions, Discovery of Nuclear Fission reactions, fission yield, delayed neutrons, Explanation of Nuclear Fission reaction based on liquid drop theory, critical size, critical energy, role of multiplication factor, basic principle of design of Atom Bomb.
Principal of design of Nuclear Reactors, Classification of nuclear reactors, Oak-Ridge Graphite Reactor, Uranium – Heavy Water Reactor, Breeder Reactor, composition, functioning and utility of these reactors, Nuclear Reactors in India, Preliminary concept of Nuclear Waste management.
Nuclear Fusion reactions, Weizäcker and Bethe cycle, Steller energy, Basic principles of design of Wet and Dry Hydrogen bombs and Cobalt bomb, Spallation reactions.
Szilard-Chalmers separation process, Hot atom Chemistry, separation of Neptunium and Plutonium from 92U238 and their nuclear reactions. Synthesis of important radioisotopes viz 1H3, 6C14, 11Na22, 15P32, 16S35, 53I131, 43Tc 99m. Their applications in predicting reaction mechanism, determination of age of rocks and minerals in agriculture, industries and uses of coordination compounds of Tc99m as imaging agents for the diagnosis of Alzheimer¢s diseases, disease related to liver, kidney, throat, bones in Nuclear medicine. Preliminary concept of damage to DNA from nuclear radiations.
Paper - IV Organometalls in organic synthesis & Coordination Chemistry.
Principle, preparations, properties and applications of the following in organic synthesis with mechanistic details.
Group I and II metal organic compounds Li, Mg, Hg, Cd and Zn compounds.
Transition metals Cu, Pd, Ni, Fe, Co and Rh compounds.
Other elements S, Si, B and Te compounds.
Symmetry operations of the molecular point groups (Oh, Td & D4h).
Point groups of following stoichiometries in coordination compounds:
MA6, MA5B, Cis- & trans-MA4B2, fac- & Mer-MA2B3
MA4, MA3B & MA2B2
MA4, MA3B, MA2B2 & MABCD
Russel Saunder’s states, Hund’s rules ground state energy terms,
Interelectron repulsion parameter, variation of Recah B & C parameter in different transition series, spin orbit coupling parameters. Spectrochemical series and effect of covalency, Nephelauxetic series.
Temperature undependent paramagnetic (TIP) behaviour.
Quenching of orbital angular momentum by ligand fields. The magnetic properties of A, E and T terms. Electron delocalization and the magnetic properties of complexes with A, E and T ground terms. Application of magnetic measurements to structure determination of transition and nontransition metal complexes.
Classification and nomenclature of macrocycles.
Type of macrocyclic ligands-design synthesis by coordination template effect. Synthesis and characterization of complexes of macrocyclic polyamines and polyether. Applications of macr ocyclic complexes.
Transition metal complexes with molecular nitrogen and molecular oxygen. Synthesis, important reactions and bonding.
Basics of photochemistry: Absorption, excitation, Frank -condon principle, Energy dissipation by radiative and non-radiative processes, quantum yield.
(i) Photosubstitution and photoaquation reactions in chromium(III)complexes.
(ii) Photosubstitution and photoredox reactions in cobalt(III) complexes.
(iii) Ligand photoreactions.
Group – B
Paper - I Organic Synthesis
Introduction. Different oxidative processes. Hydrocarbons-alkenes, aromatic rings, saturated C-H groups (activated and unactivated). Alcohols, diols, aldehydes, ketones, ketals and carboxyalic acids. Amines, hydrazines, and sulphides. Oxidations with ruthenium tetraoxide, iodobenzene diacetate and thallium (III) nitrate.
Introduction. Different reductive processes. Hydrocarbons- alkanes, alkenes, alkynes and aromatic rings. Carbonyl compounds- aldehydes, ketones, acids and their derivatives. Epoxides. Nitro, nitroso, azo and oxime groups.
General mechanistic considerations – nature of migration, migratory aptitude, memory effects. A detailed study of the following rearrangements-Pinacol-pinacolone, Wagner-Meerwein, Demjanov, Benzil-Benzilic acid, Favorskii, Arndt-Eistert synthesis, Neber, Beckmann, Hofman, Curtius, Schimdt, Baeyer-Villigr, Shapiro reaction.
Principle of protection of alcohol, amine, carbonyl and carboxyl group
Two Group C-C Disconnections.
Diels-Alder reaction, 1,3-difunctionalized compounds, a,b-unsaturated carbonyl compounds, control in carbonyl condensations, 1,5- difunctionlized compounds. Micheal addition and Robinson annelation.
Saturated heterocycles, synthesis of 3-, 4-, 5- and 6-membered rings, aromatic heterocycles in organic synthesis.
Synthesis of Some Complex molecules Application of the above in the synthesis of following compounds: Camphor, Longifoline, Cortisone, Reserpine, Vitamin D, Juvabione, Aphidicolin and Fredericamysin A.
Paper - II Heterocyclic Chemistry
Nomenclature of Heterocycles
Replacement and systematic nomenclature (Hantzsch Widman system) for monocyclic, fused and bridged heterocycles.
General chemical behaviour of aromatic heterocycles, classification (structural type), criteria of aromaticity (bond length, ring current and chemical shifts in 1H NMR-spectra, empirical resonance energy, delocalization energy and Dewar resonance energy, diamagneticsusceptibility exaltation). Heteroaromatic reactivity and tautomerism in aromatic heterocycles.
Non Aromatic Heterocycles
Strain bond angle and torsional strains and their consequences in small ring heterocycles. Conformation of six membered heterocycles with reference to molecular geometry, barrier to ring inversion, pyramidal inversion and 1,3 diaxial interaction. Stereo-electronic effects – anomeric and related effects. Attractive interactions – hydrogen bonding and intermolecular nucleophilic – electrophilic interactions.
Principles of heterocyclic synthesis involving cyclization reactions and cycloaddition reactions.
Small Ring Heterocycles
Three membered and four membered heterocycles- synthesis and reactions of aziridines, oxiranes, thiiranes, azetidines, oxetanes and thietanes.
Benzo-Fused Five-Membered Heterocycles
Synthesis and reactions including medicinal applications of benzopyrroles, benzofurans, and benzothiophenes.
General classification, chemistry, chemistry of some important meso-ionic heterocycles of type-A and B and their applications.
Six-Membered Heterocycles with One Heteroatom
Synthesis and reactions of pyrylium salts and pyrones and their comparison with pyridinium & thiopyrylium salts and pyridones. Synthesis & reactions of quinolizinium and benzopyrelium sals, coumarins and chromones.
Six-Membered Heterocycles with Two or more Heteroatoms
Synthesis and reactions of diazines, triazines, tetrazines and thiazines.
Seven and Large Membered Heterocycles
Synthesis and reactions of azepines, oxepines, thiepines, diazepines, thiazepines, diazocines, dioxocines and dithiocines.
Heterocyclic Systems Containing P, As, Sb and B
Heterocyclic rings containing phosphorous: introduction, nomenclature, synthesis and characteristics of 5- and 6-membered ring systemsphosphorinanes, phosphorines, phospholanes and phospholes. Heterocyclic rings containing As and Sb: introduction, synthesis and characteristics of 5- and 6-membered ring systems. Heterocyclic rings containing B: : introduction, synthesis, reactivity and spectral characteristics of 3-,5- and 6-membered ring systems.
Paper - III Chemistry of Natural Products
Terpenoids and Carotenoids
Classification, nomenclature, occurrence, isolation, general methods of structure determination, isoprene rule. Structure determination, stereochemistry, biosynthesis and synthesis of the following representative molecules: Citral, Geranoil, a-Terpeneol, Methol, Farnesol, Zingiberene, Santonin, Phytol, Abietic acid and B-Carotene.
Definition, nomenclature and physiological action, occurrence, isolation, general methods of structure elucidation, degradation, classification based on nitrogen heterocyclic ring, role of alkaloids in plants. Structure, stereochemistry, synthesis and biosynthesis of the following: Ephedrine, (+)-Coniine, Nicotine, Atropine, Quinine and Morphine.
Occurrence, nomenclature, basic skeleton, Diel’s hydrocarbon and stereochemistry. Isolation, structure determination and synthesis of Cholestoral, Bile acids, Androsterone, Testosterone, Estrone, Progestrone, Aldosterone. Biosynthesis of steroids
Occurrence, nomenclature and general methods of structure determination. Isolation and synthesis of Apigenin, Luteolin, Quercetin, Myrcetin, Quercetin-3-glucoside, Vitexin, Diadzein, Butein, Aureusin, Cyanidin-7-arabinoside, Cyanidin, Hirsutidin. Biosynthesis of flavonoids: Acetate pathway and Shikhimic acid pathway.
Structure and synthesis of Heamoglobin and Chlorophyll.
Prostaglandins 3 hrs
Occurrence, nomenclature, classification, biogenesis and physiological effects. Synthesis of PGE2 and PGF2a.
Pyrethroids and Rotenones
Synthesis and reactions of Pyrethroids and Rotenones. (For structure elucidation, emphasis is to be placed on the use of spectral parameters wherever possible).
Paper - IV Medicinal Chemistry
Development of new drugs, procedures followed in drug design, concept of lead Compound and ead modification, concepts of prodrugs and softdrugs,structure-activity relationship (SAR) factors affecting bioactivity, resonance,inductive effect, isosterism, bio-isosterism, spatial,consideration. Therories of drugs activity; occupancy theory, rate theory,induced fit theory. Quantitative structure activity relationship.History and development of QSAR. Concepts of drugs receptors. Elementry treatment of drug receptors.Elementry treatment of drug receptor interactions. Physico-chemical parameters; lipophilicity, partion coefficient, electronic ionization constants, steric, Shelton surface activity parameter and redox potentials. Free-Wilson analysis, relationship between free- Wilson and Hansch analysis. LD-50, ED-50 (Mathematical derivations of equations excluded).
Introduction to drug absorption , disposition, elimination using pharmacokinetics important pharmacokinetic parameters in defining drug disposition and in in therapeutics. Mention of uses of pharmacokinetics in drug development process
Introduction elementary treatment of enzyme stimulation, enzyme inhibition, sulphonamides, members active drugs, drug metabolism xenobiotics, biotransformation significance of drug medicinal chemistry.
Introduction, cancer chemotheroy, special problemes, role of alkylating agents and antimetabolites in treatment of cancer.Mention of carcinolytic antibiotics and mitotic inhibitors. Synthesis of mechlorethamine, cyclophosphamide, melphalan, uracil, mustards, and 6- mercaptopurine.Recent development in cancer hemotherapy.Hormone and natural products.
Introduction, cardiovascular diseases, drug inhibitors of peripheral sympathic function, central intervention of cardiovascular output.Direct acting arteriolar dilators. Synthesis of amyl nitrate, sorbitrate, diltiazem, quinidine, verapamil, methyldopa, tenolol,oxyprenolol.
Local Antiinfective Drugs
Introduction and general mode of action. Synthesis of sulphonamides,furrazolidone, nalidixin acid, ciproolloxacin, norfioxacin,dapsone, amino salicylic acid, isoniazid, ethionamide, ethambutal, fluconazole, econozole, griseofulvin, chkoroquin and primaquin.
Psychoactive Drugs-The Chemotherapy of mind
Introduction ,neurotransmitters, CNS depressants, general anaesthetics, mode of action hypnotics, sedatives, anti-anxity drugs ,benzodiazepines, buspirone, neurochemistry of mental diseases.Antipsychotic drugs-the neuroleptics antidepressants, butyrophenones, serendipity and drugs development,stereochemical aspects of psychotropic drugs. Synthesisof diazepam, oxazepam, chloroazepum, alprazolam phenytoin, ethosuximde, trimethadione, barbiturates, thiopental sodium, guletehimide.
Cell wall biosynthesis, inhiitors, -lactonem rings, antibiotics inhibiting protin synthesis.Synthesis of penicillin G, ampicillin, amoxicillin, chloramphenicol, cephalosporin, tetracycline and streptomycin.
Group – C
Paper - I Advanced Quantum Chemistry:
(Pre-requisite: Mathematics at least upto First year B.Sc. level is necessary. At least one PC among 4-students should be available) in future so as to undertake specified course of computer experiments.
Theoretical and Computational Treatment of Atoms and Molecules,Hartree-Fock Theory
Review of the principles of quantum mechanics, Born-Oppenheimer approximation, Slater-Condon rules, Hartree-Fock equation, Koopmans and Brillouin theories, Rothan equation.
Configuration Interaction and MC-SCF
Introduction to CI; full and truncated CI theories, size consistency. Introductory treatment of coupled cluster and MC-SCF methods.
Valence Bond and Molecular Orbital Treatment of Hydrogen Molecule/ion:
Overlap, coulamb and exchange integrals. Singlet and Triplet state of hydrogen molecule (Heitlers – London theory). Simple MO treatment of hydrogen ion for bonding and antibonding orbitals. Normalization of LCAO and MO Functions.
A review of the Huckel, EHT and PPP treatments. ZDO approximation, detailed treatment of CNDO and M INDO theories. A discussion of electronic energies and properties.
Density Functional Theory
Derivation of Hohenberg-Kohn theorem, Kohn-Sham formulation, review of the performance of the existing local (e.g. Slater Xa and other methods) and non-local functionals, treatment of chemical concepts with the density functional theory.
Paper - II Polymers:
Importance of polymers. Basic concepts: Monomers repeat units, degree of polymerization. Linear, branched and network polymers. Classification of polymers. Step Growth Polymerization: Theory of reactivity of large monomeric molecules, ring formation vs. chain formation. Polymerization: Chain Reaction, Free radical, Cationic, Anionic and living polymers. Coordination and co-polymerization. Polymerization conditions and polymer reactions.
Polydispersion-average molecular weight concept. Number, weight and viscosity average molecular weights. Polydispersity and molecular weight distribution. The practical significance of molecular weight. Measurement of molecular weights. Light scattering, osmotic, ultracentrifugation viscosity and end group analysis methods. Analysis and testing of polymers; chemical analysis, IR and NMR of polymers. X-ray diffraction study. Microscopy. Thermal analysis and physical testing hardness, tensile strength. Fatigue, impact, Tear resistance and abrasion resistance.
Structure and Properties
Morphology and order in crystalline polymer- configurations of polymer chains. Crystal structures of polymers. Morphology of crystalline polymers, strain-induced morphology, crystallization and melting. Polymer structure and property relationship. Melting point Tm, effect of chain flexibility and other steric factors. Entropy and heat of fusion. The glass transition temperature, Tg -Relationship between Tm and Tg. General ideas about elastomers, plastics and fibres.
Elastomers, Plastics and fibres: Compounding and valcanization of elastomers. Processing techniques: Calendering, die casting, rotational casting, film casting, injection moulding, blow moulding, extrusion moulding, thermoforming, foaming, reinforcing and fibre spinning.
Some Commercial and Speciality Polymers
Polyethylene, polyvinyl chloride, polyamides, polyesters, phenolic resins, epoxy resins silicone and PTFE polymers. Speciality polymers: Fire retarding polymers and electrically conducting polymers. Biomedical polymers – contact lens, dental, artificial heart, kidney, skin and blood cells – polymers.
Paper - III Chemical Dynamics:
Theories of reaction rates:
The theory of absolute reaction rates, Transmission coefficient. The review of theories of rates of unimolecular reactions . Hinshelwood Kassel Rice Rampsberger, RRKM and with special reference to slater’s theory. Thermodynamics of reaction rates.
Fast reaction Kinetics:
Relaxation phenomenon, techniques for rate measurement. T Jump, P Jump and Shock wave. The stopped flow technique. The radical detectionary mass spectrometry and laser induced magnetic resonance.
Molecular reaction dynamics:
The scope of reaction dynamics in terms of reactive encounter, energy requirement; steric requirement, diffusion controlled reactions. Material balance equation and its solution collision of structureless particles, kinetic isotope effect . The experimental observation of activated complex. Activation parameters. Reaction between ions. Dynamics of molecular collisions, Potential energy surfaces, dynamic calculation & transition state theory. Adiabatic theory of reactions.
IV. Experimental reaction dynamics:
The bulb method. The molecular beam method from the stand point of reagent specification and product distribution. The laser induced fluorescence.
Paper - IV Electrochemistry:
Electrokinetic Effects, Electrokinetic potential / Zeta potentials, Determination of zeta potential, influence of ions on electrokinetic phenomena, Electro-Osmosis, Streaming potential, Sedimentation potential. Theoretical and quantitative treatment of electrokinetic phenomena, Electrophonetic Mobility and Bound hydrogen ion.
Threshold phenomena, Donnan Membrane Equilibrium, Membrane Potential, Application of Donnan Membrance Equilibrium, Hodges-Huxely Equation, Core conductor model. Quantum Aspects of Charge transfer at electrode-solution interfaces, quantization of charge transfer tunneling. Semiconductor Interfaces: Theory of double layer semiconductor solution interfaces, Limiting current in semiconductor electrode.
Irreversible Electrode Processes:
Electrode polorization, Concept of overpotential / overvoltage, Types of overvoltage (Hydrogen overvoltage/Oxygen overvoltage), Measurement of overvoltage, Theories of overvoltage, Importance of overvoltage, Exchange current density, Phase overvoltage, Low overvoltage limit, High overvoltage limit. Passivity and its explanation, Redox Electrochemical Cells, Redox indicators.
Polarography and Voltametry:
Principle of polarography, variations of the conventional polarographic methods, Pulse Polarography, Oscillographic polarography, Tensammetry, AC polarography, square wave polarography, Anodic stripping and cyclic voltametry, Qualitative and quantitative application of polarography, Determination of stoichiometry and formation constants of complexes. Amperometric titrations and advantages.
Solid State Electrochemistry:
Solid Fuel Cells and Solid state batteries, General principles of semiconductivity and semiconductors, Temperature dependence of electrical resistances, Coherent Length, Piezoelectric effect, Piezoelectric and pyroelectric materials, Conducting polymers, Fullerenes-Doped conductors. Brief idea of Electrochemistry of molten electrolytes and nonaqueous solvents.
Paper - V Statistical thermodynamics:
Elements of Statistical Thermodynamics:
Microstates, Macrostates, Permutations and Combinations. Combinatory rule. Derivation of Lagrange’s method of undetermined multipliers. Stirling’s approximation. Partition function and its physical interpretation. Boltzmann Distribution law and its applications. Significance of b and its mathematical evaluation. Partition function and its relationship with internal energy, Helmholtz and Gibb’s free energy, entropy, enthalpy, heat capacity and pressure.
Statistical Thermodynamics of Independent Systems:
Distribution laws and their limit of applicability. Partition function for independent and distinguishable (Localised), independent and indistinguishable (Non-Localised) systems. Relation between partition function for distinguishable and indistinguishable systems. Partition function for mixture of gases. Cannonical and Grand Cannonical partition functions. Relation of Grand Cannonical partion function with thermodynamic state functions. Detailed statistical study of two phase assembly of one component system.
Applications of Statistical Thermodynamics to Chemical Systems:
Statistical interpretation of chemical equilibrium. Molecular interpretation of basic laws of thermodynamics. Statistical thermodynamics of an ideal crystal. Statistical derivation of equation of state for non-ideal fluids. Statistical thermodynamics of gaseous mixture. Statistical view of isomolecular and isotopic exchange reaction rate. Statistical evaluation of residual entropy.
Nuclear Spin – Statistics and Fluctuations:
Symmetry and nuclear spin, ortho and para nuclear states, ortho and para hydrogen, Nuclear spin extended to special cases. Mean Distribution and Mean Square Deviation. Fluctuations in energy in a Cannonical ensemble, Fluctuations in density, radioactive disintegration and Brownian movement.