PAPER‐I
Atomic Structure
- Heisenberg’s uncertainty principle Schrodinger wave equation (time independent)
- Interpretation of wave function
- particle in one- dimensional box
- quantum numbers
- hydrogen atom wave functions
- Shapes of s, p and d orbitals.
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.
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, semiconductors.
The Gaseous State and Transport Phenomenon
- Equation of state for 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.
Liquid State
- Kelvin equation
- Surface tension and surface energy, wetting and contact angle, interfacial tension and capillary action.
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, -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.
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.
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
- overpotential; electroanalytical techniques : amperometry, ion selective electrodes and their use.
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.
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 reaction on heterogeneous catalysts.
Bio-inorganic Chemistry
Metal ions in biological systems and their role in ion-transport across the membranes (molecular mechanism), oxygen-uptake proteins, cytochromes and ferredoxins.
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; carboxylate 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.
Main Group Chemistry
Boranes, borazines, phosphazenes and cyclic phosphazene, silicates and silicones, Interhalogen compounds; Sulphur—nitrogen compounds, noble gas compounds.
General Chemistry of ‘f’ Block Element
Lanthanides and actinides: separation, oxidation states, magnetic and spectral properties; lanthanide contraction.
PAPER-II
Delocalized Covalent Bonding
Aromaticity, anti-aromaticity; annulenes, azulenes, tropolones, fulvenes, sydnones.
Different Reactions
- Reaction mechanisms : General methods (both kinetic and non-kinetic) of study of mechanisms or organic reactions : isotopes, method cross-over experiment, intermediate trapping, stereochemistry; energy of activation; thermodynamic control and kinetic control of reactions.
- Reactive intermediates : Generation, geometry, stability and reactions of carbonium ions and carbanions, free radicals, carbenes, benzynes and nitrenes.
- Substitution reactions :—SN 1, SN 2, and SN i, mechanisms ; neighbouring group participation; electrophilic and nucleophilic reactions of aromatic compounds including heterocyclic compounds—pyrrole, furan, thiophene and indole.
- Elimination reactions :—E1, E2 and E1cb mechanisms; orientation in E2 reactions—Saytzeff and Hoffmann; pyrolytic syn elimination—acetate pyrolysis, Chugaev and Cope eliminations.
- Addition reactions :— Electrophilic addition to C=C and C≡C; nucleophilic addition to C=O, C≡N, conjugated olefins and carbonyls.
- Reactions and Rearrangements
- Pinacol-pinacolone, Hoffmann, Beckmann, Baeyer-Villiger, Favorskii, 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 reactions.
- 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.
- 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.
Synthetic Uses of Reagents
- OsO4, HlO4, CrO3, Pb(OAc)4, SeO2, NBS, B2H6, Na-Liquid NH3, LiAIH4, NaBH4, n-BuLi, MCPBA.
- Photochemistry :—Photochemical reactions of simple organic compounds, excited and ground states, singlet and triplet states, Norrish-Type I and Type II reactions.
Spectroscopy
Principle and applications in structure elucidation
Rotational—Diatomic molecules; isotopic substitution and rotational constants.
- Vibrational—Diatomic molecules, linear triatomic molecules, specific frequencies of functional groups in polyatomic molecules.
- Electronic—Singlet and triplet states. N conjugated double bonds and conjugated carbonyls Woodward-Fieser rules; Charge transfer spectra.
- Nuclear Magnetic Resonance (1H NMR): Basic principle; chemical shift and spin-spin interaction and coupling constants.
- Mass Spectrometry :—Parent peak, base peak, metastable peak, McLafferty rearrangement.