Pg trb syllabus - Chemistry

 Chemistry

Unit-I 

Periodic properties – Atomic radius – ionic radius, ionization potential, electron affinity and electronegativity – Their significance in chemical bonding. VB theory, MO theory – applications – Comparision of VB and MO theories – VSEPR theory – Bond order – Bond energy – Bond length Bond polarity – Partial ionic character of bonds – The concept of multicentre bond – Electron deficient compounds – Hydrogen bond – Its influences. Non aqueous solvents – A general study of typical reactions in non aquieous media – comparison with reactions in aqueous media. Solid state chemistry – Ionic bonding – Lattice energy – Born equation – Born Haber cycle – Radius ratio rule – Born Meyer equation – Kapustinski’s Modification – energetics of the dissolution of ionic compounds in polar solvents – different types of electostatic interactions. Structural aspects of solids – Fourier synthesis and analysis structure factors – scattering factors – Spinels and Inverse spinels – defects in stoinchiometric and Non stoichiometric crystals. Electrical properties of solids – Band theory semi conductors – Junction devices – Super conductivity – Ionic conductivity – Optical properties of solids – Lasers and phosphors – Photovoltaic effect – solar energy. Magnetic properties of solids – Different types – dia, para, ferro, antiferro and ferri Magnetism – Magnetic hysteresis. 

Unit II 

 Co-ordination chemistry – Methods of preparation of complexes – isomerism in complexes – applications of complex formation in analytical chemistry – complexes and their stability chelate effect Stability constants – Their determination – complexes of Metals in different oxidation states and their stability. Optical activity and concept of chirality – Different kinds of opticalloy active compounds – configuration – Foscher, sawhorse and Newman projections – Absolute configuration R and S Notations – Methods with more than one chiral center – Asymmetric synthesis – optical purity

Geometrical isomerism resulting from double bonds – The E.Z. system of nemenclature – Geometrical isomerism of monocyclic compounds and fused ring systems – 

Sterospecific and stereo selective reactions with examples. 

 Confermational analysis – conformation and reactivity in acylic and cyclo – hexane 

systems – conformation of decalins, cyclohexane and cyclohexanone. 

Unit III 

 Organic reaction mechanisms – General methods of investigating reaction mechanisms – kinetic and non-kinetic methods – different types of reaction intermediates. 

 Aliphatic nucleophilic substituion SN1, SN2 and SNi reactions – substitution at 

vinylic and benzylic carbon – stereo chemistry of nucleophilic reaction – solvents and substituent effects – Nucleophilicity Neighboring group participation. 

 Addition to double and triple bonds – Mechanism Hydration – Hydroboration – 

Hydroxiylation – epoxidation. 

 Elimination reactions E1, E2, E1cB Mechanism – Orientation effects in elimination 

reactions – stereo chemistry of elimination reactors - dehydration of alcohols – dehydro 

halogenation – cope elemination. 

 Heterocyclics – synthesis and reactivity of furan, thiophene, pyrrole pyridine, 

quinoline, isoquinoline, Indole, flavenes, and anthocyanins – skraup synthesis – Fischer indole synthesis. 

 The chemistry ; of natural products structure elucidations and Biogenesis of the following: 

Alkaloids : Reticulene, Reserpine, Morphine 

Terpenoids : Zingiberene, Squalene, Lanosteroal 

Steroids : Cholesterol, Oestrone, Progresterone 

Carbohydrates: Maltose, Starch, Cellulose (biogenis not expected) 

Structure and functions of biopolymer such as proteins and Nucleic acids – 

Primary, Secondary and tertiary structures of proteins – Mechanism of Enzyme action – DNA and RNA.

Unit IV 

 The old quantum theory – Inadequacy of classical mechanics – Failure of classical 

mechanics – success of quantum hypothesis explaining black body radiation – Photo electric effect – the hydrogen spectrum – Bohr’s explanation of hydrogen spectrum – Failure of Bohr’s model. 

 De broglie’s postulates of Matter waves – experimental observation of matter 

waves – Heisenberg’s uncertainly principle – wave particle dualism – Davisson, Garmer 

experiments – Postulates of quantum mechanics – Time dependent schrodinger equation – Needs of an acceptable wave function – Physical significance of Psi function. 

 Operators in quantum mechanics. Operator algebra – Linear and Hermitian 

operators –m Eigen functions and Eigen values – Hamiltonian operators – Angular momentum. 

 Application of schrodinger equation – particle in one and three dimensional boxes – quantum mechanical results for a simple harmonic oscillaltor and rigid rotator - approxination methods – perturbation methods – variation method – VB and MO methods.  Symmetry elements and symmetry operations – Point groups – representation of groups reducible and irreducible representations characters tables – Orthogonality theorem and its consequences. 

 Symmetry selection rule for IR and Ramanspectra – Systematic procedure for 

determining symmetries of normal modes of vibration – symmetry applied to MO theory and orbital hybridization. 

Unit V 

 Thermodynamic equations of state – closed and open systems – partial molal 

quantities – chemical potential with temperature and pressure – third law of thermodynamics. 

 Fugacity – methods of determination – activity and activity co-efficient – 

standard states for gases, liquids – solids and solutions – mean activity co-efficients of electrolytes. 

Maxwell’s distribution of molecular velocities – derivation of expression for 

average, most probable and rcot mean square velocities – Microstates Macrostates – partial 

functions – Sackur tetrode equation – statistical approach to the third law of Thermodynamics – 

Maxwell Boltzmann – Bose Einstein and Fermi

Dirace statistics – Heat capacities of solids – Einstein and Debye Models Low temperature – Negative absolute temperature. 

 Chemical equilibrium – thermodynamic derivation of equilibrium constant – standard free energy – calculations. 

 Phase equilibrium – thermodynamic derivation of phase rule application of phase rule – three component systems. 

 Chromotography – column, paper, thinlayer, gas-liquid, High pressure liquid 

chromatography HPLC principle and applications. 

 Thermal analysis – different thermal analysis (DTA) – Principle and applications 

– thermogravimetric analysis (TGA) Principle and application. 

 Chemical crystallography – Diffraction methods – X ray Neutron, electron 

diffraction methods. Principle and applications. 

Polarimetry – Circular ichroism – Optical Rotatory dispersion (ORD) Principle and applications. 

Unit VI 

 Nuclear – chemistry – Nuclear nadii spin and moments – Nuclear structure – 

Nuclear forces – Nuclear stability – Nuclear modes – Modes of Radioactivity decay. Nuclear 

isomerisation Nuclear Reaction Energy – Coulomb barrier cross section – excitation function – 

Radiactive Equiliberia – Types of Neclear reactions – Nuclear fision Nuclear Reactors – Atomic 

Power Project in India – Radiation hazards – Radiation desimetry – Nuclear fusion – Stellar energy. 

 Application of Radioactivity – Tracer Techniques – Neutron - Activation 

analysis – Isotope Dilution Analysis – Interaction of radiation with matter – Range of alpha and beta particles – Absorption co-efficient,. 

 Orgnometallic compounds – Metallecences – Arene complexes – Nonaromatie 

olefins and acetylenes complexes – catalysis by organometallic compounds Wilkinson’s catalyst 

– Oxoprocess – wecker process – Ziegler – Natta catalysis. 

 Inorganic photo chemistry – Photochemical reactions of coordination and organ 

metallic compounds – Properties of excited states – charge transfer photo Oxidation, photo reduction, photo substitution, photo isomerisation - Photo chemical conversion – Solar energy. 

Unit VII 

 Term symbols and term states – Dn - ions energy levels – Diagrams weakfield 

and strong field and strong field concepts – spin orbit coupling – The Nephelanxetic effect 

charge transfer spectra – Applications of UV, IR, NMR, BSR and mossbaver spectroscopy 

techniques in the study of co-ordination chemistry. 

 Magnetic interactions – Magnetic susceptibilities determination – application in 

co-ordination chemistry. Application of VB, MO, CF and LF theories in co-ordination chemistry 

– Group theoretical approach – splitting of d-orbitals – spectro-chemical series – concept of 

weak and strong fields – Thermodynamic and chemical effect of d-orbitals splitting – Jahn Teller distortion. 

 Nuclear Magnetic Resonance Spectroscopy – Theory – Study of PMR – 

chemical shift – Type of shielding – Spin-spin coupling spin decoupling – spplications to simple natural products. 

Electron spin resonance spectro scopy – paramagnetism – Nuclear hyperfine structure – Hyperfine coupling. 

Unit VIII 

Huckel’s rule and concept of aromaticity – aromaticity of Benzenoid – 

Nonbenzenoid aromatics. The annulenes - Aromaticity in charged rings and fused ring systems. 

Aromatic electrophilic substitution – Mechanism and reactivity, Typical reactions to include 

diazonium coupling – Halognation, sulphonation. Friedal craft alkylation and acylation. 

Aromatic Nucleophilic substitution – Benzyne mechanism – Examples. Oxidation – Reduction 

reactions – Mechanisms – selectivity in oxidations and reductions. 

 Molecular rearrangements – Rearrangements with Carbon to Nitrogen, Carton 

to Oxygen and Carbon migrations. Curtivs, Lossen, Schmitts Baeyer – Villiger, Pinacol – 

Pinacolene, Benzoil – Benzilicacid, Benzidine, Favorski and fries rearrangements – sigmatropic 

rearragements – claisen and cope. Pericyclic reactions, selection rules – orbital symmetry – 

Electrocyclic reactions – cycle additions sigmatropic reactions. 

 Modern synthetic reactions – Diels alder reaction witting reactions – stork 

Enamine reactions – Mannich reactions, Birch reductions. 

Unit IX 

 Theories of reaction rates – simple collision theory – absolute reaction rate 

theory (ARRT) – Reaction co-ordinate – Potential energy surfaces. Hammett – Taft equation – 

Hammett acidity function – Acid base catalysis Bronsted relation Enzyme catalysis – Michaelis 

Menton Law – influence of PH and temperature. Surface phenomenon – Heterogeneous 

catalysis – Absorption isotherms. Electrolytic conductance – applications – solubility product – 

Interionic attraction theory – Debye – Huckel – Onsager equation – equivalent conductivity of electro lytes. 

 Electro potentials – Electrochemical cells – electrode – electrolyte interface – 

electrical double layer electro capillary phenomena – electro kinetic Phenomena – Membrane 

potential – Polarisation – over potential – Polarography – concentration polarization – electro 

chemical polarization – sutler – Volmer equation. 

Unit X 

 Theory and applications of the following spectroscopic methods; electonics 

spectra-UV-Visible spectra – IR spectra – Raman spectra – Laser – Raman spectra – NMR – 

WCR- ESR Spectra – Mossbaver spectro scopy – photoelectron spectro scopy – Polymerisation 

reactions – Mechanism – sterochemical aspects. Types of polymers – organic and inorganic 

polymers – preparation – properties – structure – polystyrene – Polyvinylchloride – Polyesters – 

Nylon – Phenol resin – amino resins – epoxy resins. Phosphonitrilic compounds – silicons – 

Borazines applications of polymers