1.Reaction Mechanism of Transition Metal Complexes
Energy profile of a reaction, reactivity of metal complexes , inert and labile complexes, kinetic application of valence bond and crystal field theories, kinetics of octahedral substitution, acid hydrolysis, factors affecting acid hydrolysis, base hydrolysis, conjugate base mechanism, direct and indirect evidence in favor of conjugate mechanism, anationreactions, reactions without metal ligand bond cleavage.
2.Substitution reactions in square planer complexes, the trans effect, mechanism of the substitution reaction; Redox reactions, electron transfer reactions, mechanism of one electron transfer reactions, outer-sphere type reactions, cross reactions and Marcus-Hush theory, inner sphere type reactions.
3.Metal Clusters – Higher Boranes, carboranes, metalloboranes and metallo carboranes, metal clusters (carbonyl and halide) and compound with metal – metal multiple bonds (Binuclear and trinuclear).
4.Electronic Spectra and Magnetic Properties of Transition Metal complexes
Spectroscopic ground states, correlation, Orgel and Tanabe-Sugano energy diagrams for transition metal complexes (d1to d9 states) Calculations of Dq. B and b parameters,
Charge transfer spectra, spectroscopic method of assignment of absolute configuration in optically active metal chelates and their stereo-chemical information, anomalous magnetic moments, magnetic exchange coupling and spin crossover.
CHE-C 222 : Organic Chemistry
60 Hours (4 Hr/per Week)
Aliphatic Electrophilic Substitution
Bimolecular mechanism-SE2 and SE1. The SE1 mechanism, electrophilic substitution accompanied by double bond shifts.Effects of substrates, leaving group and the solvent polarity on the reactivity.
Aromatic Electrophilic Substitution
The arenium ion mechanism, orientation and reactivity, energy profile diagrams. The ortho/para ratio, hipso-attack, orientation in other ring systems.Quantitative treatment of reactivity in substrates and electrophiles. Diazonium coupling.Vilsmeir reaction, Gattermann-Koch reaction.
Aromatic Nucleophilic Substitution
The SNAr, SN1, benzyne and SRN1 mechanism. Reactivity-effect of substrate structure, leaving group and attacking nucleophile. The Richter, Sommelet- Hauser and Smiles rearrangements.
Conformational analysis of cycloalkanes, decalins, effect of conformation on reactivity, conformation of sugars, steric strain due to unavoidable crowding.
Elements of symmetry, chirality, molecules with more than one chiral center, threo and erythro isomers, methods of resolution, optical purity, enantiotopic and diastereotopic atoms, groups and faces, stereo specific and stereo selective synthesis. Asymmetric synthesis. Optical activity in the absence of chiral carbon (biphenyls, allenes and spiranes,) chirality due to helical shape. Stereochemistry of the compounds containing nitrogen, sulphur and phosphorus.
Addition to Carbon-Carbon Multiple Bonds.
Mechanistic and stereo chemical aspects of addition reactions involving electrophiles, nucleophiles and free radicals, regio- and chemo- selectivity, orientation and reactivity.Addition to cyclopropane ring. Hydrogenation of double and triple bonds, hydrogenation of aromatic rings. Hydroboration. Michael reaction. Sharpless asymmetric epoxidation.
The E2, E1 and E1CB mechanisms and their spectrum. Orientation of the double bond . Reactivity - effects of substrate structures. Attacking base, the leaving group and the medium. Mechanism and orientation in pyrolytic elimination. Claisen and Cope rearrangements. Fluxional tautomerism. Ene reactions.
Molecularorbital symmetry. Frontier Orbitals of ethylene, 1,3-butadiene, 1,3,5-hexatriene and allyl system. Classification of Pericyclic reactions.Woodward-Hoffmann correlation diagrams. FMO and PMO approach. Electro-cyclic reactions- con-rotatory and dis-rotatory motions, 4n, 4n+2 systems, Cycloadditions- antra-facial and supra-facial additions, 4n, 4n+2 systems, 2,2+2 addition of ketenes and 1,3 dipolar cyclo-additions,Sigma tropic rearrangements- suprafacial and antarafacial shifts of H-, sigma tropic shifts involving carbon moieties, 3,3- and 5.5. sigma tropic rearrangements.
CHE-C 223 : PhysicalChemistry
60 Hours (4 Hr/per Week)
Ordinary angular momentum, generalized angular momentum, eigenfunctions for angular momentum, eigenvalues of angular momentum, operators using ladder operators, addition of angular moments, spin, antisymmetry and Pauli exclusion principle.
BElectronic Structure of Atoms
Electronic configuration.Russell-Saunders terms and coupling schemes, Slater-Condon parameters, term separation energies of the pn configuration, term separation energies for the dn configurations, magnetic effects: spin-orbit coupling and Zeeman splitting introduction to the methods of self consistent field, the virial theorem.
2.Phase Equilibria :
Application of phase rule to three component systems: Graphical representation, Solid-liquid equilibrium, Liquid-liquid equilibrium,
Second order phase transitions :
3. Statistical Thermodynamics
A.Concept of distribution, thermodynamic and probability and most probable distribution. Ensemble averaging, postulates of ensemble averaging. Canonical, grand canonical and micro canonical ensembles, corresponding distribution laws (using Lagrange's method of undetermined multipliers).
B.Partition functions- translational, rotational, vibrational electronic partition functions, calculation of thermodynamic properties in terms of partitionfunctions.Applications ofpartition functions.
Heat capacity behaviour of solids- chemical equilibrium constant in termsof partition. Femi-Dirac statistics, distribution law and applications to metal. Bose-Einstein statistics- distribution law and application to helium.
4.Non Equilibrium Thermodynamics
Thermodynamic criteria for non-equilibrium states, entropy production and entropy flow, entropy balance equations for different irreversible processes (i.e. heat flow, chemical reaction etc.) fluxes and forces, non equilibrium stationary states, phenomenological equations, microscopic reversibility and Onsager's reciprocity relations, electro-kinetic phenomena, diffusion, electric conduction, irreversible thermodynamics for biological systems, coupled reactions.
A.Dynamic chain(hydrogen-bromine reaction, pyrolysis of acetaldehyde, decomposition of ethane). Photochemical( Zhabotinsky reaction). Homogeneous catalysis, kinetics of enzyme reactions, general features of fast reactions, study of fast reactions by flow method, relaxation method, flash photolysis and the nuclear magnetic resonance method. Dynamics of molecular motions, probing the transition state, dynamics of barrierless chemical reactions in solution, dynamics of unimolecular reactions ( Lindemann- Hinshelwood and Rice-Ramsperger- Kassel-Marcus - RRKM theories of unimolecular reactions ).
A.Polymer-definition, types of polymers, electrically conducting, fire resistant, liquid crystal polymers, kinetics of polymerization, mechanism of polymerization.
B.Molecular mass, number and mass average molecular mass, molecular mass determination (osmometry, viscometry, diffusion and light scattering methods) sedimentation, chain configuration macromolecules, calculation of average dimension of various chain structures.
A.Semiconductor interfaces- theory of double layer at semiconductor, electrolyte solution interfaces, structure of double layer interfaces. Effect of light at semiconductor solution interface.
B.Electrocatalysis- interfaceof various parameters. Hydrogen electrode.
C.Polarography theory, Ilkovic equation; half wave potential and its significance.
Introduction to corrosion, homogenous theory, forms of corrosion, corrosion monitoring and prevention methods.
CHE-C 224 : Spectroscopy and Diffraction Methods
45Hours (3 Hr/per Week)
Energy levels, molecular orbitals, vibronic transitions, vibrational progression and geometry of the excited states, Frank Condon principle, electronic spectra of polyatomic molecules, emission spectra, radiative and non radiative decay, internal conversion, spectra of transition metal complexes, charge transfer spectra.
2.Magnetic Resonance Spectroscopy
A.Nuclear Magnetic Resonance Spectroscopy
Nuclear spin, nuclear resonance, saturation, shielding of magnetic nuclei, chemical shift, factors influencing chemical shift, deshielding, spin-spin interaction, factors 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 and its advantages, use of NMR in medical diagnostics.
B.Electron Spin Resonance Spectroscopy
Basic principles, Zero field splitting and Kramer's degeneracy, factors affecting the ‘g’ value. Isotropic and anisotropic hyperfine constant, spin Hamiltonian, spin densities and McConnell relationship, measurement techniques, applications.
C.Nuclear Quadrupole Resonance Spectroscopy
Quadrupole nuclei, quadrupole moments, electric field gradients, coupling constants, splitting, applications
Basic principles of photoacoustic spectroscopy(PAS), PAS gases and condensed systems, chemical and surface applications.
4.X - RAY Diffraction
A.Braggs condition, Miller Indices, Laue method, Bragg method, Debye – Scherr method of X-ray structural analysis of crystals, index reflections, identification of unit cell from systematic absences in diffraction pattern. Structure of simple lattices and X-ray intensities, structure factor and its relation to intensity and electron density, phase problem. Description of the procedure for an X-ray structure analysis, absolute configuration of a molecules, Ramchandran diagrams.
Scattering intensity vs scattering angle, Wierl equation, measurement technique, elucidation of structure of simple gas phase molecules, low energy electron diffraction and structure of surfaces.
Scattering of neutrons by solids and liquids, magnetic scattering, measurement techniques, Elucidation of structure of magnetically ordered unit cell.
CHE-C 225 : Computers for Chemists
60 Hours (4 Hr/per Week)
Introduction to computers and computing
Basic structure and functioning of computers with a PC as an illustrative example. Memory, I/O devices. Secondary storage. Computer languages. Operating systems with DOS as an example. Introduction to Unix and Windows, data processing, principles of programming. Algorithms and flow charts.
Computer programming in FORTRAN/ C/ BASIC
(The language features are listed here with respect to FORTRAN. The instructoir may choose another language such as BASIC or C and the features mey be replaced appropriately). Elements of the computer language. Constants and variables. Operations and symbols. Expresion. Arithmetic assignment ststement. Input and Out put . Format statement. Termination statement. Branching statements such as IF or GO TO statements. LOGICAL variables. Double precision variables. Subscripted variables and DIMENSION. DO statement. FUNCTION and SUBROUTINE. COMMON and DATA ststements.(Note: Students learn these programming logics by “hand on ” experience on a personnel computer ).
3.Programming in Chemistry :
Development of small computer codes involving simple formulae inchemistry, such as van der Waal equation, pH titration, kinetics, radioactive decay. Evaluation of lattice energy and ionic radii from experimental data. Linear simultaneous equation to solve secular equation with Huckel theory. Elementary structural features such as bond lengths, bond angles, dihedral angles etc of molecules extracted from a data base such Cambrige data base.
a.Use of Computer Programmes :
The students will learn to how to operate a PC and how to run stsndard programmes and packages. Execution of linear regression such as X Y plot, numerical integration and differentiation as wel as differential equation solution programmes. Monte Carlo and molecular dynamics. Programmes with datapreferably from physi9cal chemistry laboratory. Further, the students will operate one or two or more packages such as MATLAB, EASYPLOT, EXCEL, FOXPRO and Word Processing software – MS Word and Powerpoint.
CHE-C 226 : Laboratory Exercise : Inorganic
Separation of Cations and Anions by
(b).Column chromatography – ion exchange.
Preparation of selected inorganic compounds
8.cis – [Co(trien)(NO2]Cl.H2O
Interpretation of pre recorded spectra of complexes – electronic, IR, ESR, Thermograms (TGA)
CHE-C 227 : Laboratory Exercise :ORGANICCHEMISTRY
Organic Synthesis :
Acetoacetic acid ester condensation: Synthesis of ethyl n-butylacetonatoacetate by AEE condensation.
Cannizziro reaction : 4-Chlorobenzaldehyde as substrate,
Friedel Crafts Reaction ; b-benzoylpropionic acid from succinic anhydride and benzene, Aromatic electrophilic substitutions : Synthesis of p-nitroaniline and p-bromoaniline.
The products may be Characterized by Spectral Techniques.
Determination of the precentage or number of hydroxyl groups in an organic compound by acetylation method.
Estimation of amines / phenols using bromate solution / or acetylation method.
1.Determination of the Velocity constant, order of reaction and energy of activation for soponification of ethylacetate by sodium hydroxide conductometrically.
2.Determination of solubility and solubility product of sparingly soluble salts (e.g. PbSO4, BaSO4) conductometrically.
3.Determination of the strength of strong and weak acids in a given solution by conductometry.
4.To study the effect of solvent on the conductance of AgNO3 /acetic acid and to determine the degree of dissociation and equilibrium constant in different solvents and their mixtures (DMSO, DMF, dioxane, acetone, water) and to test the validity of Debye-Huckel-Onsager theory.
5.Determination of activity coefficient of Zn ions in the solution of 0.002 M ZnSO4 using Debye-Huckel’s limiting law.
B. Potentiometry / pH metry
i.Determination of strengths of halides in a mixture potentiometrically.
ii.Determination of valency of mercurous ions potentiometrically.
iii.Determination of the strength of strong acid and weak acids in a given mixture using potentiometer / pH meter.
iv.Determination of the temperature dependence of EMF of a cell.
v.Determination of the formation constant of silver-ammonia complex and stoichiometry of the complex potentiometerically.
vi.Acid-base titration in a non-aqueous media using a pH meter.
vii.Determination of activity and activity coefficient of electrolytes.
viii.Determination of dissociation constant of acetic acid in DMSO, DMF, acetone and dioxane by titrating it with KOH.
ix.Determination of thermodynamic constants DG, DH, DS for the reaction by e.m.f. method.
Zn+ H2SO4à ZnSO4 + 2H .
ICH -C 229Lab Course – Computers
15 Hrs (1 periodper week)
The students will learn to how to operate a PC and how to run standard programmer and packages – for chemistry applications.
Execution of linear regression such as X Y plot, numerical integration and differentiation as well as differential equation solution programmer .
Monte Carlo and molecular dynamics – PC Model, Programming with data preferably from physical chemistry laboratory-Basic/C/Fortran.
Operation of one or two or more packages such as EXCEL, Word Processing software – MS Word and Powerpoint,MATLAB, EASYPLOT, FOXPRO.
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.