CHEMISTRY

PAPER- I

1. 1. Atomic Structure:  

Heisenberg’s uncertainty principle, Schrödinger wave equation (time independent): Interpretation of wave function. Particle in one –dimensional box, quantum numbers, hydrogen atoms wave functions: Shapes of s, p and d orbitals.

1. 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, concept of resonance and resonance energy; molecular orbital theory (LCAO method); bonding H2+, H2 He2 + to Ne2, NO, CO, HF, CN-, Comparison of valence bond and molecular orbital theories, bond order, bond strength and bond length.
2. Solid State:-
   Crystal systems: Designation of crystal faces, lattice structures and unit cell; Bragg’s law; X-ray diffraction by crystals; Close packing, radius ratio rules, calculation of some limiting radius ratio values; structures of NaCl, ZnS, CsCl, CaF2; Stoichiometric and nonstoichiometric defects, impurity defects, semi-conductors.
3. The Gaseous State and Transport Phenomenon:
   Equation of state real gases, intermolecular interactions, and critical phenomena and liquefaction of gases; Maxwell’s distribution of speeds, intermolecular collisions, collisions on the wall and effusion; Thermal conductivity and viscosity of ideal gases.
4. Liquid State:
   Kelvin equation: Surface tension and surface energy. Wetting and contact angle. Interfacial tension and capillary action.
5. 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, effect and inversion temperature; criteria for equilibrium, relation between equilibrium constant and thermodynamic quantities; Nernst heat theorem, introductory ideal of third law of thermodynamics.
6. Phase Equilibria and Solutions:
   Clausius-Clapeyron equation; phase diagram for a pure substance; phase equilibria in binary systems, partially miscible liquids-upper and lower critical solution temperatures; partial molar quantities, their significance and determination; excess thermodynamic functions and their determination.
7. 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 cell and it applications fuel cells ad batteries.
   Processes at electrodes; double layer at the interface; rate of charge transfer, current density; over potential; electro analytical techniques; amperometry, ion selective electrodes and their use.
8. Chemical Kinetics:
   Differential and integral rate equations for zeroth, first, second and fractional order reactions; Rate equations involving reverse, parallel, consecutive and chain reactions; effect of temperature and pressure on rate constant. Study of fast reactions by stop-flow and relaxation methods. Collisions and transition state theories.
9. Photochemistry:
   Absorption of light: decay of excited state by different routes; photochemical reactions between hydrogen and halogens and their quantum yields.
10. Surface Phenomena and Catalysis:
    Adsorption from gases and solutions on solid adsorbents; Langmuir and B.E.T. adsorption isotherms; determination of surface area, characteristics and mechanism of reactions on heterogeneous catalysts.
11. Bio-inorganic Chemistry:
    Metal ions in biological systems and their role in ion-transport across the membranes (molecular mechanism), oxygen –uptake proteins, cytochromes and ferrodoxins.
12. Coordination Chemistry:
    Bonding in transition of metal complexes. Valence bond theory, crystal field theory and its modifications; applications of theories in the explanation of magnetism and electronic spectra of metal complexes.Isomerism in coordination compounds: IUPAC nomenclature of coordination compounds; stereochemistry of complexes with 4 and 6 coordination numbers; chelate effect and polynuclear complexes; trans effect and its theories; kinetics of substitution reactions in square –planar complexes; thermodynamic and kinetic stability of complexes.EAN rule. Synthesis structure and reactivity of metal carbonyls; carbonylate anions, carbonyl hydrides and metal nitrosyl compounds.

    Complexes with aromatic systems, synthesis, structure  and bonding in metal olefin complexes, alkyne complexes and cyclopentadienyl complexes; coordinative-unsaturation, oxidative addition reactions, insertion reactions, fluxional molecules and their characterization; compounds with metal-metal bonds and metal atom clusters.

13. Main Group Chemistry:
    Boranes, borazines, phosphazenes and cyclic phosphazene, silicates and silicones, Interhalogen compounds; Sulphur-nitrogen compounds, noble gas compounds.
14. General Chemistry of ‘f’ Block Element:
    Lanthanides and actinides: separation, oxidation states, magnetic and spectral properties; lanthanide contraction.

PAPER –II

1. 1. Delocalized Covalent Bonding:
      Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, fulvenes, sydnones.
   2. (i)  Reaction Mechanism:  General methods (both kinetic and non-kinetic) of study of mechanisms of organic reactions: isotopic method, crossover experiment, intermediate trapping, stereochemistry; energy of activation; thermodynamic control and kinetic control of reactions.(ii)  Reaction Intermediates:  Generation, geometry, stability and reactions of Carbonium ions and carbanions, free radicals, carbenes, benzynes and nitrenes,(iii) Substitution Reactions:- –SN1. SN2. And SNi. Mechanisms, neighboring group participation; electrophilic and nucleophilic reaction of aromatic compounds including heterocyclic compounds-pyrrole, furan, thiophene and indole.

      (iv)  Elimination Reactions:-  E1, and E2 and E1 cb mechanisms; orientation in E2 reactions Saytzeff and Hoffmann; pyrolytic syn elimination –acetate pyrolysis, Chugaev and Cope eliminations.

      Addition Reaction:- Electrophilic addition to C=C and     C≡C nucleophilic addition to C=O, C ≡ N, conjugated olefins and carbonyls.

      Reactions and Rearrangements:-
      (a) Pinacol-pinacolone, Hoffmann, Beckmann, Baeyer-Villiger, Favorski, Fries, Claisen, Cope, Stevens and Wagner-Meerwein rearrangements.
      Aldol condensation, Claisen condensation, Dieckmann. Perkin, Knoevenagel, Witting, Clemmensen, Wolff-Kishner, Cannizzaro and von Richter reactions; Stobbe, benzoin and acyloin condensations; Fischer indole synthesis, Skraup synthesis, Bischler Napieralski, Sandmeyer, Reimer-Tiemann and Reformatsky reactiosns.

   3. Pericyclic Reactions:-
      Classification and examples; Woodward –Hoffmann rules-Electrocyclic  reactions, cycloaddition reactions [2+2 and 4+2] and sigmatropic shifts [1,3;3, 3 and 1, 5], FMO approach.
   4. (i) Preparation and Properties of Polymers:  Organic polymers polyethylene. Polystyrene, polyvinyl chloride, Teflon, nylon, terylene, synthetic and natural rubber.
      (ii). Biopolymers; structure of proteins, DNA and RNA.
   5. Synthetic Uses of Reactions:
      OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na Liquid NH3, LiAIH4, NaBH4 n-BuLi, MCPBA.
   6. Photochemistry:-
      Photochemical reactions of simple organic compounds, excited and ground states, singlet and triplet states, Norrish Type I and Type II reactions.
   7. Spectroscopy:–
      Principle and applications in structure elucidation.
      (i) Rotational – Diatomic molecules; isotopic substitution and rotational constants.
      (ii)Rotational – Diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules.
      Electronic – Singlet and triplet states transitions; application to conjugated double bonds and conjugated carbonyls Woodward –Fieser rules; Charge transfer spectra.