PAPER - I
PART - A
Unit I Solid State Chemistry :
Classification of solids, Seven crystal systems, elements of symmetry in crystals, space lattice and unit cell, classification of crystals on the basis of bond types, Ionic solids, metallic solids and molecular solids. The close Packing of spheres, Hexagonal close packing, cubic close packing and body centered cubic packing, coordination number and radius ratio effects. Bragg’s
Law of X-ray diffraction, powder pattern method, crystal structure of NaCl, KCl, ZnS, CsCl, and CaF2
Phase Equilibria:
Phases, components, degrees of freedom, phase diagram of one and two component systems, Nernst distribution Law, applications of distribution law.
Unit II The Gaseous State and Transport Phenomenon:
Equation of State for real gases, intermolecular interactions and critical phenomena and liquefaction of gases, Maxwell’s distribution law of molecular velocities, evaluation of average rms; most probable velocity and average kinetic energy from Maxwell equation. Degrees of freedom, principle of equipartition of energy and molecular basis of heat capacity
Thermodynamics:
Work, heat and internal energy; first law of thermodynamics.
Second law of thermodynamics; entropy as a state function, entropy changes in various processes, entropy–reversibility and irreversibility, Free energy functions; Thermodynamic equation of state; Maxwell relations; Temperature, volume and pressure dependence of U, H, A, G, Cp and Cv, á and â; J-T effect and inversion temperature; criteria for equilibrium, relation between equilibrium constant and thermodynamic quantities; Nernst heat theorem, introductory idea of third law of thermodynamics.
Unit III Surface Chemistry :
Stability and origin of charge on colloids, electrokinetic potential. Physical and chemical adsorption, various types of adsorption isotherms, homogeneous and heterogeneous catalysis, Enzyme catalysis (Michelis-Menton) equation.
Electrochemistry:
Debye-Huckel theory of strong electrolytes and Debye-Huckel limiting Law for various equilibrium and transport properties.
Galvanic cells, concentration cells; electrochemical series, measurement of e.m.f. of cells and its applications fuel cells and batteries.
Processes at electrodes; double layer at the interface; rate of charge transfer, current density; over potential; electro-analytical techniques: Polarography, amperometry, ion selective electrodes and their uses.
Unit IV Chemical Kinetics:
Differential and integral rate equations for zeroth, first, second and fractional order reactions;
Rate equations involving reverse, parallel, consecutive and chain reactions; branching chain and explosions; effect of temperature and pressure on rate constant; Study of fast reactions by stop-flow and relaxation methods;
Collisions and transition state theories.
Photochemistry:
Absorption of light; decay of excited state by different routes; photochemical reactions between hydrogen and halogens and their quantum yields.
PART - B
Unit I Atomic Structure:
Bohr Model and its limitations, DeBroglie Equation, Heisenberg’s uncertainty principle, Quantum mechanical operators and the Schrodinger wave equation (time dependent), physical significance of wave function and its characteristics (normalised, orthogonal), Radial distribution and shapes of s, p, d and f orbitals. Particle in One Dimensional Box, Quantization of electronic energies (Qualitative treatment of hydrogen atom). Pauli’s exclusion principle, Hund’s rule of maximum multiplicity, Aufban principle, Electronic configuration of atoms, Long form of periodic table including Translawrencium elements. Periodicity in properties of the elements such as atomic and ionic radii, ionization potential, electron affinity, electronegativity and hydration energy.
Nuclear and Radiation Chemistry:
Structure of nucleus (Shell Model), Nuclear forces, nuclear stability - N/P ratio, nuclear binding energy, Detection and measurement of radioactivity, Artificial transmutation of elements and nuclear reactions, nuclear fission and fusion, Radioactive isotopes and their applications, Radio carbon dating,
Units of radioactivity.
Unit II Chemical Bonding:
Ionic bond, characteristics of ionic compounds, lattice energy, Born-Haber cycle; covalent bond and its general characteristics, polarities of bonds in molecules and their dipole moments; Valence bond theory (Heitier – London and Pauling-Slater-theories), Hybridization, VSEPR Theory and shapes of simple inorganic molecules, Molecular Orbital theory, Bonding, Non-bonding Molecular orbitals, Molecular orbital energy. Lever diagrams for Homo and Hetero nuclear diatomic molecules. Bond order and Bond length and bond strength. Sigma and pi-bonds, Hydrogen bond.
Bio-inorganic Chemistry:
Essential and trace elements in biological processes, metallaporphyrins with special reference to Haemoglobin and Myoglobin, Biological role of alkali and alkaline earth metal ions with special reference to Ca2+.
Unit III Chemistry of s- and p- Block Elements :
General properties of s- and p- block elements, chemical reactivity of elements and group trends.
Chemical behaviour with respect to their hybrids, halides and oxides.
Chemistry of Transition elements :
General characteristics, variable oxidation states, complex formation, colour, magnetic and catalytic properties. Comparative study of 4d and 5d transition elements with 3d analogues with respect to their ionic radii, oxidation states and magnetic properties.
Unit IV Chemistry of Lanthanides and Actinides:
Lanthanide contraction, oxidation states, Principles of separation of Lanthanides and Actinides, magnetic and spectral properties of their compounds.
Coordination Chemistry:
Preparation, properties and uses of the following:
Inorganic Compounds: Heavy water, Boric acid, diborane, hydrazine, hydroxylamine, Potassium dichromate, Potassium Permanganate, Ce(IV) Sulphate, and Ti (III) Sulphate.
Polymers : Molecular weight of polymers by sedimentation, light scattering, viscosity and osmotic pressure. Number average and weight average molecular weights, elasticity and crystallinity of polymers.
Borazines : Silicates and silicones and Phosphonitrilic halide polymers.
PAPER-II
PART - A
Unit I Delocalised covalent bonding : Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, kekulene, fulvenes, sydnones. Reactions and Rearrangements : (a) Pinacol-pinacolune, Hoffmann, Beckmann, Baeyer Villiger, Favorskii, Fries, Claisen, Cope, Stevens and Wagner-Meerwein rearrangements. (b) Aldol condensation, Claisen condensation, Dieckmann, Wolff-Kishner, Cannizzaro and von Ritcher reactions; Stobbe, benzoin and acyloin condensations; Fischer indole synthesis, Skraup synthesis, Bischler-Napieralski, Sandmeyer, ReimerTiemann and reformatsky reactions.
Unit II (i) Reaction mechanisms : General methods (both kinetic and nonkinetic) of study of mechanism or organic reactions illustrated by examples, use of isotopes, cross-over experiment, intermediate trapping, stereochemistry; energy diagrams of simple organic reactions. Transition states and intermediates; energy of activation; thermodynamic control and kinetic control of reactions.
(ii) Reactive intermediates : Generation, geometry, stability and reactions of carbonium and carbonium ions, carbanions, free radicals, carbenes, benzynes and niternes.
(iii) Substitution reactions: SN1, SN2, SNi, SN1/, SN2/, SNi/ and
SRN1 mechanisms; neighbouring group participation; electrophilic and nucleophilic reactions of aromatic compound including simple heterocyclic compounds¡-pyrrole, furan thiophene and indole.
(iv) Elimination reactions : E1, E2 and E1cb mechanism; orientation in E2 reactions-Saytzeff and Hoffmann; pyrolytic syn elimination¡-acetate pyrolysis, Chugaev and Cope eliminations.
(v) Addition reactions : Electrophilic addition to C=C and C=C; nucleophilic addition to C=O, C=N, conjugated olefins and carbonyls.
Unit III Pericyclic reactions: Classification and examples; WoodwardHoffmann rules¡-electrocyclic reactions, cycloaddition reactions [2+2 and 4+2] and sigmatropic shifts [1, 3; 3, 3 and 1, 5] FMO approach.
Unit IV Preparation and Properties of Polymers: Organic polymerspolythene, polystyrene, polyninyl chloride, Teflon, nylon, terylene, synthetic and natural rubber.(ii) Biopolymers; Structure of proteins, DNA and RNA.
PART - B
Unit I Synthetic uses of reagents: OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiA1H4 NaBH4 n-BuLi, MCPBA.
Unit II Photochemistry: Photochemical reactions of simple organic compounds, excited and ground states, singlet and triplet states, Norrish-Type I and Type II reactions.
Unit III Spectroscopy: Principle and applications in structure elucidation:
(i) Rotational-Diatomic molecules; isotopic substitution and rotational constants.
(ii) Vibrational -Diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules.
(iii) Raman Spectre: Raman Effect, stokes and antistokes lines and their intensity difference, Rules of Mutual exclusion.
Unit IV (i) Electronic: Singlet and triplet states. N¡V>¡Vƒá* and ƒá>* transitions; application to conjugated double bonds and conjugated carbonyls
Woodward-Fieser rules; Charge transfer spectra.
(ii) Nuclear Magnetic Resonance (1HNMR) : Basic principle; chemical shift and spin interaction and coupling constants.
(iii) Mass Spectrometry : Parent peak, base peak, metastable peak, McLafferty rearrangement.
