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 in H2+,
H2, He2+ to Ne2, NO, CO,
HF, and 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 and CaF2;
Stoichiometric and nonstoichiometric defects, impurity defects, semi-conductors.
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
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, a and b;
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.
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
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:
Polarography, amperometry, ion selective electrodes and their uses.
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: Absorption 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 Compounds: (i) Bonding theories 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.
(ii) 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.
(iii) EAN rule, Synthesis structure and reactivity of metal carbonyls;
carboxylate anions, carbonyl hydrides and metal nitrosyl compounds.
(iv) 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 Elements: Lanthanides
and actinides; separation, oxidation states, magnetic and spectral properties;
(i) Reaction Mechanisms: General methods (both kinetic
and non-kinetic) of study of mechanism of organic reactions: isotopic
method, cross-over experiment, intermediate trapping, stereochemistry;
energy of activation; thermodynamic control and kinetic control of reactions.
(ii) Reactive 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; neighbouring group participation; electrophilic
and nucleophilic reactions of aromatic compounds including heterocyclic
compounds–pyrrole, furan, thiophene and indole. (iv) Elimination Reactions: E1, E2 and E1cb mechanisms;
orientation in E2 reactions–Saytzeff and Hoffmann; pyrolytic syn
elimination – Chugaev and Cope eliminations. (v) Addition Reactions: Electrophilic addition to C=C
and C=C; nucleophilic addition to C=0, C=N, conjugated olefins and carbonyls.
(vi) Reactions and Rearrangements: (a) Pinacol-pinacolone,
Hoffmann, Beckmann, Baeyer–Villiger, Favorskii, Fries, Claisen,
Cope, Stevens and Wagner-Meerwein rearrangements.
(b) 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
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]
(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.
Synthetic Uses of Reagents: OsO4, HIO4,
CrO3, Pb(OAc)4, SeO2, NBS, B2H6,
Na-Liquid NH3, LiAlH4, NaBH4, n-BuLi
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: (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) Electronic: Singlet and triplet states; n -->
p* and p p*
--->transitions; application to conjugated double bonds and conjugated
carbonyls–Woodward-Fieser rules; Charge transfer spectra. (iv) Nuclear Magnetic Resonance (1H NMR):
Basic principle; chemical shift and spin-spin interaction and coupling
constants. (v) Mass Spectrometry: Parent peak, base peak, metastable
peak, McLafferty rearrangement.