1. Atomic structure
Quantum theory, Heisenberg's uncertainity principle, Schrodinger wave
equation (time independent).
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Interpretation of wave function, particle in
one-dimensional box, quantum numbers, hydrogen atom wave functions. Shapes of s,
p and d orbitals.
2. Chemical bonding
Ionic bond, characteristics of ionic compounds, factors affecting stability
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 in homonuclear molecules: H2+,
H2 to Ne2, NO, CO, HF, CN, CN�, BeH2 and CO2. Comparison of valence bond
and molecular oribtal theories, bond order, bond strength and bond length.
3. Solid State
Forms of solids, law of constancy of interfacial angles, crystal systems and
crystal classes (crystallographic groups). Designation of crystal faces, lattice
structures and unit cell. Laws of rational indices. Bragg's law. X-ray
diffraction by crystals. Close packing, radious ratio rules, calculation of some
limiting radius ratio values. Structures of NaCl, ZnS, CsCl, CaF2, CdI2 and
rutile. Imperfections in crystals, stoichiometric and nonstoichiometric defects,
impurity defects, semi-conductors. Elementary study of liquid crystals.
4. The gaseous state
Equation of state for real gases, intermolecular interactions, liquefictaion
of gases and critical phenomena, Maxwell's distribution of speeds,
intermolecular collisions, collisions on the wall and effusion.
5. Thermodynamics and statistical thermodynamics
Thermodynamic systems, states and processes, work, heat and internal energy;
first law of thermodynamics, work done on the systems and heat absorbed in
different types of processes; calorimetry, energy and enthalpy changes in
various processes and their temperature dependence.
Second law of thermodynamics; entropy as a state function, entropy changes in
various process, entropy�reversibility and irreversibility, Free energy
functions; criteria for equilibrium, relation between equilibrium constant and
thermodynamic quantities; Nernst heat theorem and third law of thermodynamics.
Micro and macro states; canonical ensemble and canonical partition function;
electronic, rotational and vibrational partition functions and thermodynamic
quantities; chemical equilibrium in ideal gas reactions.
6. Phase equilibria and solutions
Phase equilibria in pure substances; 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 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�voltameter, polarography, ampero-metry, cyclic-voltametry, ion
selective electrodes and their use.
8. Chemical kinetics
Concentration dependence of rate of reaction; defferential 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 hydrogn and halogens and their quantum yields.
10. Surface phenomena and catalysis
Absorption from gases and solutions on solid adsorbents, adsorption
isotherms,�Langmuir and B.E.T. isotherms; determination of surface area,
characteristics and mechanism of reaction on heterogeneous catalysts.
11. Bio-inorganic chemistry
Metal ions in biological systems and their role in ion-transport across the
membranes (molecular mechanism), ionophores, photosynthesis�PSI, PSII; nitrogen
fixation, oxygen-uptake proteins, cytochromes and ferredoxins.
12. Coordination chemistry
(a) Electronic configurations; introduction to theories of bonding in
transition metal complexes. Valence bond theory, crystal field theory and its
modifications; applications of theories in the explanation of magnetism and
electronic spactra of metal complexes.
(b) 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-planer complexes; thermodynamic and
kinetic stability of complexes.
(c) Synthesis and structures of metal carbonyls; carboxylate anions, carbonyl
hydrides and metal nitrosyl compounds.
(d) 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. General chemistry of �f� block elements
Lanthanides and actinides; separation, oxidation states, magnetic and
spectral properties; lanthanide contraction.
14. Non-Aqueous Solvents
Reactions in liquid NH3, HF, SO2 and H2 SO4. Failure of solvent system
concept, coordination model of non-aqueous solvents. Some highly acidic media,
fluorosulphuric acid and super acids.
Paper-II
1. Delocalised covalent bonding : Aromaticity, anti-aromaticity;
annulenes, azulenes, tropolones, kekulene, fulvenes, sydnones.
2(a) Reaction mechanisms : General methods (both kinetic and
non-kinetic) 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.
(b) Reactive intermediates : Generation, geometry, stability and
reactions of carbonium and carbonium ions, carbanions, free radicals, carbenes,
benzynes and niternes.
(c) 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, indole.
(d) Elimination reactions : E1, E2 and E1cb mechanism; orientation in
E2 reactions�Saytzeff and Hoffmann; pyrolytic syn elimination�acetate
pyrolysis, Chugaev and Cope eliminations.
(e) Addition reactions : Electrophilic addition to CC and C=C;
nucleophilic addition to C=O, CN, conjugated olefins and carbonyls.
(f) Rearrangements : Pinacol-pinacolune, Hoffmann, Beckmann,
Baeyer�Villiger, Favorskii, Fries, Claisen, Cope, Stevens and Wagner-Meerwein
rearrangements.
3. Pericyclic reactions : Classification and examples;
Woodward-Hoffmann rules�clectrocyclic reactions, cycloaddition reactions [2+2
and 4+2] and sigmatropic shifts [1, 3; 3, 3 and 1, 5] FMO approach.
4. Chemistry and mechanism of reactions : Aldol condensation
(including directed 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.
5. Polymeric Systems
(a) Physical chemistry of polymers : Polymer solutions and their
thermodynamic properties; number and weight average molecular weights of
polymers. Determination of molecular weights by sedimentation, light scattering,
osmotic pressure, viscosity, end group analysis methods.
(b) Preparation and properties of polymers : Organic
polymers�polyethylene, polystyrene, polyvinyl chloride, Teflon, nylon, terylene,
synthetic and natural rubber. Inorganic polymers�phosphonitrilic halides,
borazines, silicones and silicates.
(c) Biopolymers : Basic bonding in proteins, DNA and RNA.
6. Synthetic uses of reagents : OsO4, HIO4, CrO3, Pb(OAc)4, SeO2, NBS,
B2H6, Na-Liquid NH3, LiA1H4 NaBH4 n-BuLi, MCPBA.
7. Photochemist : Photochemical reactions of simple organic compounds,
excited and ground states, singlet and triplet states, Norrish-Type I and Type
II reactions.
8. Principles of spectroscopy and applications in structure elucidation
(a) Rotational spectra�diatomic molecules; isotopic substitution and
rotational constants.
(b) Vibrational spectra�diatomic molecules, linear triatomic
molecules, specific frequencies of functional groups in polyatomic molecules.
(c) Electronic spectra : Singlet and triplet states. N�>* and �>*
transitions; application to conjugated double bonds and conjugated
carbonyls�Woodward-Fieser rules.
(d) Nuclear magnetic resonance : Isochronous and anisochronous
protons; chemical shift and coupling constants; Application of H1 NMR to simple
organic molecules.
(e) Mass spectra : Parent peak, base peak, daugther peak, metastable
peak, fragmentation of simple organic molecules; cleavage, McLafferty
rearrangement.
(f) Electron spin resonance : Inorganic complexes and free radicals.
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